CN116770323A - Iridium single-site modified cobalt spinel electrocatalytic material and electrocatalyst - Google Patents
Iridium single-site modified cobalt spinel electrocatalytic material and electrocatalyst Download PDFInfo
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- CN116770323A CN116770323A CN202210233074.4A CN202210233074A CN116770323A CN 116770323 A CN116770323 A CN 116770323A CN 202210233074 A CN202210233074 A CN 202210233074A CN 116770323 A CN116770323 A CN 116770323A
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 54
- 239000011029 spinel Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 50
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 40
- 150000001868 cobalt Chemical class 0.000 title claims abstract description 27
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 15
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims abstract description 45
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- -1 iridium unit modified cobalt Chemical class 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000011812 mixed powder Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000713 high-energy ball milling Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011363 dried mixture Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 8
- 229910000457 iridium oxide Inorganic materials 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000003321 amplification Effects 0.000 description 4
- 238000004630 atomic force microscopy Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003991 Rietveld refinement Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
Abstract
The invention provides an iridium unit modified cobalt spinel electrocatalytic material and an electrocatalyst, belonging to the field of inorganic materials, and having the following characteristics: the chemical formula of the iridium single-site modified cobalt spinel electrocatalytic material is abbreviated as: ir-Co 3 O 4 Iridium in the iridium single-site modified cobalt spinel electrocatalytic material exists in the form of single sites in the cobalt spinel.
Description
Technical Field
The invention relates to the field of inorganic materials, in particular to an iridium unit modified cobalt spinel electrocatalytic material and an electrocatalytic agent.
Background
Hydrogen has larger energy density and zero carbon emission, and is a clean and sustainable energy source capable of effectively solving the crisis of fossil energy at present. Electrochemical water splitting is considered one of the most promising routes to hydrogen energy. There are two half reactions in the electrolytic water reaction cell, respectively a hydrogen evolution reaction of the cathode and an oxygen evolution reaction of the anode, wherein the oxygen evolution reaction is considered to be a major bottleneck limiting the overall reaction efficiency due to having a large overpotential and a slow reaction kinetics rate. Therefore, the development of an efficient electrocatalyst for accelerating the oxygen precipitation reaction of the anode has important significance for improving the efficiency and popularizing and applying the electrochemical water decomposition device.
Currently, there are two types of electrochemical oxygen precipitation reaction catalysts which are concerned, one type is iron, cobalt and nickel-based non-noble metal oxide materials, and the catalyst has the advantages of rich storage, low cost and certain catalytic activity. However, these oxide materials are very soluble under acidic conditions and therefore have poor catalytic stability. The other type is noble metal catalysts such as ruthenium and iridium, which can effectively improve the catalytic performance of oxygen precipitation reaction as an electrocatalyst, but the large-scale application of the noble metal is seriously hindered due to the high price and the rare reserves of the noble metal. Therefore, the combination of high catalytic performance and low cost is a major requirement for developing oxygen evolution reaction electrocatalysts at present.
The single-atom/single-site catalyst has the advantages of uniform active site distribution, wide carrier range, high atom utilization efficiency, small noble metal consumption and the like in electrochemical reaction, and has been widely paid attention to scientific researchers in recent years.
Disclosure of Invention
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide an iridium-single-site modified cobalt spinel electrocatalytic material and an electrocatalyst.
The invention provides an iridium unit modified cobalt spinel electrocatalytic material, which has the following characteristics: the chemical formula of the iridium single-site modified cobalt spinel electrocatalytic material is abbreviated as: ir-Co 3 O 4 Iridium in the iridium single-site modified cobalt spinel electrocatalytic material exists in the form of single sites in the cobalt spinel.
The iridium unit point modified cobalt spinel electrocatalytic material provided by the invention can also have the characteristics that the iridium unit point modified cobalt spinel electrocatalytic material has a nano-sheet structure, the thickness of the nano-sheet structure is 2-4 nm, and the atomic ratio of Ir, co and O in the iridium unit point modified cobalt spinel electrocatalytic material is 1.05:27.43:71.52.
the iridium unit modified cobalt spinel electrocatalytic material provided by the invention can also have the characteristics that the preparation method comprises the following steps: step 1, cobalt chloride hexahydrate, anhydrous iridium chloride and sodium chloride are initially and uniformly mixed in an agate mortar to obtain mixed powder; step 2, grinding the mixed powder and adding sodium hydroxide solution to obtain a mixture; and 3, drying the mixture in an oven, grinding the dried mixture in an agate mortar, then placing the mixture in a muffle furnace to react for a preset time at a preset temperature, washing and drying to obtain the iridium single-point modified cobalt spinel electrocatalytic material.
The iridium unit modified cobalt spinel electrocatalytic material provided by the invention can also have the following characteristics: in the step 1, the mol ratio of cobalt chloride hexahydrate to anhydrous iridium chloride serving as a precursor is 20:1.
The iridium unit modified cobalt spinel electrocatalytic material provided by the invention can also have the following characteristics: in the step 1, the mass ratio of cobalt chloride hexahydrate to sodium chloride is 476 mg/500 mg.
The iridium unit modified cobalt spinel electrocatalytic material provided by the invention can also have the following characteristics: the specific process of the step 2 is as follows:
the mixed powder is placed in a high-energy ball milling tank for ball milling for 1 hour at 500rpm, then sodium hydroxide solution is added, the mixed powder is continuously placed in the high-energy ball milling tank for ball milling for 1 hour at 500rpm, the concentration of the sodium hydroxide solution is 4M, and the mass volume ratio of the mixed powder to the sodium hydroxide solution is (0.9 g-1.1 g): 1mL.
The iridium unit modified cobalt spinel electrocatalytic material provided by the invention can also have the following characteristics: wherein, in step 3, the mixture is dried in an oven at a temperature of 60 ℃ for 12 hours.
The iridium unit modified cobalt spinel electrocatalytic material provided by the invention can also have the following characteristics: in the step 3, the preset temperature is 350 ℃, the preset time is 6 hours, and the sintering gas in the muffle furnace is air.
The invention provides an electrocatalyst, which is characterized by comprising: the iridium single-site modified cobalt spinel electrocatalytic material and carbon powder.
In the electrocatalyst provided by the invention, it may also have the following features: the electrocatalyst is prepared by grinding and mixing cobalt spinel electrocatalytic materials modified by iridium units and carbon powder according to a mass ratio of 1:1.
Effects and effects of the invention
The iridium single-site modified cobalt spinel electrocatalytic material (chemical formula is Ir-Co 3 O 4 ) Because iridium exists in the cobalt oxide spinel structure in a single-site mode, the atom utilization rate of noble metal iridium is maximized, and meanwhile, the single-site iridium serves as a main active site and has a synergistic effect with surrounding cobalt atoms, so that an electronic structure can be effectively regulated, the oxygen precipitation performance of the material is improved, and the design of the structure realizes that the cobalt spinel has higher oxygen precipitation catalytic activity under an acidic condition and has wide application prospect.
In addition, because of Ir-Co 3 O 4 The catalyst has an ultrathin sheet structure, so that more iridium single sites can be exposed on the surface, and meanwhile, a larger active surface area is provided for the contact of electrolyte and the catalyst, and the oxygen precipitation catalysis performance of the catalyst can be effectively improved.
In addition, the Ir-Co is used as the catalyst 3 O 4 And the electrocatalyst prepared by mixing carbon powder shows high catalytic activity in oxygen precipitation reaction.
In addition, because of the Ir-Co 3 O 4 The preparation method adopts simple grinding and calcining processes to prepare, and the precursor cobalt chloride hexahydrate and the anhydrous iridium chloride are nontoxic and easy to obtain, so that Ir-Co 3 O 4 The preparation method has the advantages of safety, reliability, simplicity, high efficiency, easy amplification and the like, and can synthesize gram-scale catalyst at one time.
Furthermore, because the preparation method is adopted, the cobalt spinel electrocatalytic material modified by iridium unit with high activity (the chemical formula is abbreviated as Ir-Co) can be prepared by only adding the doping amount of the noble metal precursor iridium chloride 3 O 4 ) Therefore, the invention has low cost and the likeAdvantages are achieved.
Drawings
FIG. 1 is a drawing of example 1 (Ir-Co 3 O 4 ) X-ray diffractometer (XRD) and simulated patterns;
FIG. 2 is a schematic diagram of example 1 (Ir-Co 3 O 4 ) Atomic Force Microscopy (AFM);
FIG. 3 is a drawing of example 1 (Ir-Co 3 O 4 ) Scanning electron microscopy (SEM-EDX);
FIG. 4 is a schematic diagram of example 1 (Ir-Co 3 O 4 ) Spherical aberration correcting transmission electron microscopy (AC-HRTEM);
FIG. 5 is a drawing of example 1 (Ir-Co 3 O 4 ) An extended X-ray absorption fine structure spectrum (EXAFS);
FIG. 6 is comparative example 1 (Co 3 O 4 ) X-ray diffractometer (XRD) and simulated patterns; FIG. 7 is a schematic diagram of example 1 (Ir-Co 3 O 4 ) Compared with comparative example 1 (Co 3 O 4 ) Comparative example 2 (IrO) 2 ) Comparative example 3 (C-Co) 3 O 4 ) An oxygen evolution performance graph corresponding to the sample in 0.5M sulfuric acid electrolyte;
FIG. 8 is a drawing of example 1 (Ir-Co 3 O 4 ) Compared with comparative example 1 (Co 3 O 4 ) Comparative example 2 (IrO) 2 ) Comparative example 3 (C-Co) 3 O 4 ) Electrochemical impedance spectrogram and fitting curve of corresponding sample;
FIG. 9 is a drawing of example 1 (Ir-Co 3 O 4 ) Comparative example 1 (Co) 3 O 4 ) Comparative example 2 (IrO) 2 ) Comparative example 3 (C-Co) 3 O 4 ) Corresponding sample at 10mA/cm 2 Constant current timing potential test patterns at current density;
FIG. 10 is a drawing of example 1 (Ir-Co 3 O 4 ) Photo after amplification experiment;
FIG. 11 is a drawing of example 1 (Ir-Co 3 O 4 ) X-ray diffractometer (XRD) after performing the magnification experiment.
Detailed Description
In order to make the technical means, creation characteristics, achievement purposes and effects of the invention easy to understand, the following examples specifically describe the iridium unit modified cobalt spinel electrocatalytic material, the preparation method thereof and the electrocatalyst according to the present invention with reference to the accompanying drawings.
Example 1 ]
This example 1 provides an iridium single site modified cobalt spinel electrocatalytic material (Ir-Co 3 O 4 ) The preparation method comprises the following steps:
step 1, 0.476g of cobalt chloride hexahydrate, 0.029g of anhydrous iridium chloride and 0.5g of sodium chloride are put into an agate mortar to be ground and uniformly mixed, thereby obtaining mixed powder.
And 2, placing the mixed powder obtained in the step 1 in a high-energy ball milling tank for ball milling for 1 hour at 500rpm, then adding 1mL of 4M sodium hydroxide solution, and then continuously placing the mixed powder in the high-energy ball milling tank for ball milling for 1 hour at 500rpm to obtain a mixture.
Step 3, placing the mixture obtained in the step 2 in an oven, drying at 60 ℃ for 12 hours to obtain black brown powder, then placing in a muffle furnace, reacting at 350 ℃ for 6 hours to obtain black powder, washing the black powder with ultrapure water four times at room temperature, and drying in a vacuum drying oven to obtain the iridium unit point modified cobalt spinel electrocatalytic material (Ir-Co 3 O 4 ) The structural formula is shown in figure 1.
Comparative example 1 ]
This comparative example 1 provides a pure cobalt spinel material (Co 3 O 4 ) The preparation method comprises the following steps:
grinding 0.476g of cobalt chloride hexahydrate and 0.5g of sodium chloride in an agate mortar to obtain uniformly mixed powder; placing the uniformly mixed powder in a high-energy ball milling tank for ball milling for 1 hour at 500 rpm; after ball milling is completed, adding 1mL of 1M sodium hydroxide solution into the obtained uniform powder, and then continuously placing the uniform powder into a high-energy ball milling tank for ball milling for 1 hour at 500 rpm; and (3) placing the mixture obtained after ball milling in an oven, and drying at 60 ℃ for 12 hours to obtain black brown powder. Then placing in a muffle furnace, reacting for 6h at 350 ℃ to obtain black powder, washing with ultrapure water four times at room temperature, and drying in a vacuum drying oven to obtain pure cobalt spinel (Co) 3 O 4 )。
Comparative example 2 ]
Comparative example 2 employed a commercial iridium oxide catalyst (IrO) 2 ) Purchased from Innochem, beijing Inocover technologies, inc., 99.9% purity.
Comparative example 3 ]
Comparative example 3 employed a commercial tricobalt tetraoxide catalyst (C-Co 3 O 4 ) Purchased from Innochem, beijing Inocover technologies, inc., 99.5% purity.
Test example 1 ]
Characterization by X-ray diffraction
The compounds prepared in example 1 and comparative example 1 were subjected to X-ray diffraction. The characterization results are shown in fig. 1, 6 and 11.
FIG. 1 shows a process of example 1 (Ir-Co) 3 O 4 ) X-ray diffractometer (XRD) and simulated patterns.
As shown in FIG. 1, ir-Co 3 O 4 The structural refinement of (C) is that Ir-Co is obtained after refinement by the Rietveld method (Rietveld, 1969) 3 O 4 The space group is Fd-3m. Finishing results show that the side lengths of a, b and c of the unit cell after single-point iridium doping are 8.097, and the unit cell volume is 530.89. The experimental spectrum after structural refinement is well matched with the calculated spectrum.
FIG. 6 is comparative example 1 (Co 3 O 4 ) X-ray diffractometer (XRD) and simulated patterns.
As shown in FIG. 6, co 3 O 4 The structural refinement of (C) is performed by the Rietveld method (Rietveld, 1969), co is obtained after refinement 3 O 4 The space group is Fd-3m. The finishing result shows that the side lengths of a, b and c of the unit cell after the single-point iridium doping are 8.075, the unit cell volume is 526.61, and the unit cell volume is smaller than Ir-Co 3 O 4 . This means Ir-Co 3 O 4 In which single-site iridium was successfully incorporated into cobalt spinel. The experimental spectrum after structural refinement is well matched with the calculated spectrum.
FIG. 11 is a drawing of example 1 (Ir-Co 3 O 4 ) X-ray diffractometer (XRD) after performing the magnification experiment.
As shown in FIG. 11, example 1 (Ir-Co 3 O 4 ) After the amplification experiment, the sample is well matched with PDF standard card PDF#74-1656, which shows that Ir-Co 3 O 4 Still has good crystallinity after amplification, and the structure is unchanged.
Test example 2 ]
Atomic force microscope map characterization
FIG. 2 is a schematic diagram of example 1 (Ir-Co 3 O 4 ) Atomic Force Microscopy (AFM).
As shown in FIG. 2, ir-Co in example 1 3 O 4 Having a nanoplatelet structure with a thickness of about 3nm, indicating Ir-Co 3 O 4 The catalyst has an ultrathin sheet structure, is beneficial to exposing active sites and increases the contact area of the catalyst and electrolyte.
Test example 3 ]
Scanning electron microscope energy spectrum element analysis
FIG. 3 is a drawing of example 1 (Ir-Co 3 O 4 ) Scanning electron microscopy (SEM-EDX).
As shown in FIG. 3, ir-Co in example 1 3 O 4 The atomic ratio of Ir/Co/O was 1.05/27.43/71.52, indicating that the noble iridium content was very small.
Test example 4 ]
Spherical aberration correction transmission electron microscope characterization
FIG. 4 is a schematic diagram of example 1 (Ir-Co 3 O 4 ) Is a spherical aberration correcting transmission electron microscopy image (AC-HRTEM).
As shown in FIG. 3, the white circles are shown in example 1 (Ir-Co 3 O 4 ) Is an iridium atom in (a). It can be seen that the iridium atoms are present singly and uniformly dispersed in the cobalt spinel, indicating that iridium is present in the cobalt spinel in the form of a single site.
Test example 5 ]
Extended X-ray absorption fine structure spectrum characterization
FIG. 5 is a drawing of example 1 (Ir-Co 3 O 4 ) Is an extended X-ray absorption fine structure spectrum (EXAFS).
As shown in FIG. 5, example 1 (Ir-Co 3 O 4 ) Only iridium-oxygen bonds and iridium-cobalt bonds are present in the iridium species in (a) indicating that iridium is present in the cobalt spinel in the form of a single site.
Test example 6 ]
Catalytic Performance testing of materials
Ir-Co obtained in example 1 was taken 3 O 4 And carbon powder (50% by mass: 50%) were placed in a glass bottle, 1900 μl of isopropanol was added, and then mixed ultrasonically in an ultrasonic machine for 2 hours. Adding 100 microliter of Nafion (5 wt.%) into the obtained mixed solution, continuing to carry out ultrasonic treatment for 30 minutes, uniformly carrying out ultrasonic treatment, then taking a proper amount of the mixed solution, coating the mixed solution on the surface of a glassy carbon electrode, drying at room temperature, and controlling Ir-Co 3 O 4 The loading was 0.255mg/cm 2 . The catalytic properties of the material were characterized by an electrochemical workstation.
The pure cobalt spinel (Co) obtained in comparative example 1 was taken 3 O 4 ) Carbon black (50% by mass: 50%) was added to the flask, 1900. Mu.l of isopropanol was added thereto, and the mixture was sonicated in an sonicator for 2 hours. Adding 100 microliter of Nafion (5 wt.%) into the obtained mixed solution, continuing to carry out ultrasonic treatment for 30 minutes, uniformly carrying out ultrasonic treatment, then taking a proper amount of the mixed solution, coating the mixed solution on the surface of a glassy carbon electrode, drying at room temperature, and controlling Co 3 O 4 The loading was 0.255mg/cm 2 . The catalytic properties of the material were characterized by an electrochemical workstation.
Commercial Iridium oxide (IrO) purchased in comparative example 2 was taken 2 ) Carbon black (50% by mass: 50%) was added to the flask, 1900. Mu.l of isopropanol was added thereto, and the mixture was sonicated in an sonicator for 2 hours. Adding 100 microliter of Nafion (5 wt.%) into the obtained mixed solution, continuing to carry out ultrasonic treatment for 30 minutes, uniformly carrying out ultrasonic treatment, then taking a proper amount of the mixed solution, coating the mixed solution on the surface of a glassy carbon electrode, drying at room temperature, and controlling IrO (infrared radiation) 2 The loading was 0.255mg/cm 2 . The catalytic properties of the material were characterized by an electrochemical workstation.
Commercial tricobalt tetraoxide (C-Co) purchased in comparative example 3 was taken 3 O 4 ) Carbon black (50% by mass: 50%) was added to the flask, 1900. Mu.l of isopropanol was added thereto, and the mixture was sonicated in an sonicator for 2 hours. To the resulting mixed solution, 100. Mu.l of Nafion (5 wt.%Continue ultrasonic for 30 minutes, uniformly take a proper amount of the mixed solution to be coated on the surface of the glassy carbon electrode after ultrasonic treatment, dry at room temperature, and control C-Co 3 O 4 The loading was 0.255mg/cm 2 . The catalytic properties of the material were characterized by an electrochemical workstation.
The model of the carbon powder used in the test example is Vulcan XC-72R.
The test results are shown in FIGS. 7-9.
FIG. 7 shows the structure of example 1 (Ir-Co 3 O 4 ) And the polarization curves of the oxygen evolution reactions of the catalysts prepared in comparative examples 1-3 in 0.5M sulfuric acid electrolyte.
As shown in FIG. 7, ir-Co 3 O 4 The prepared catalyst has the minimum overpotential and the optimal oxygen precipitation reaction performance.
FIG. 8 shows the structure of example 1 (Ir-Co 3 O 4 ) And the catalysts prepared in comparative examples 1-3 were tested for electrochemical impedance spectroscopy and fitted with a curve.
As shown in FIG. 8, ir-Co 3 O 4 The prepared catalyst exhibits minimal electrochemical impedance, and is proved to have the fastest reaction kinetic rate and electron transport capacity.
FIG. 9 is a drawing of example 1 (Ir-Co 3 O 4 ) And the catalysts prepared in comparative examples 1 to 3 were at 10mA/cm 2 A stability graph of the constant current chronopotentiometric test was performed at the current density of (c).
As shown in FIG. 9, ir-Co 3 O 4 The catalyst prepared was at 10mA/cm 2 Exhibits the most excellent stability at the current density of (3).
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (10)
1. An iridium single-site modified cobalt spinel electrocatalytic material is characterized in that:
wherein, the chemical formula of the iridium unit modified cobalt spinel electrocatalytic material is abbreviated as: ir-Co 3 O 4 ，
The iridium in the iridium single-site modified cobalt spinel electrocatalytic material exists in the cobalt spinel in a single-site form.
2. The iridium single-site modified cobalt spinel electrocatalytic material of claim 1, wherein:
wherein the iridium unit-point modified cobalt spinel electrocatalytic material has a nano-sheet structure, the thickness of the nano-sheet structure is 2 nm-4 nm,
the atomic ratio of Ir, co and O in the iridium single-site modified cobalt spinel electrocatalytic material is 1.05:27.43:71.52.
3. the iridium single-site modified cobalt spinel electrocatalytic material as claimed in claim 1 or 2, wherein the preparation method thereof comprises the following steps:
step 1, cobalt chloride hexahydrate, anhydrous iridium chloride and sodium chloride are initially and uniformly mixed in an agate mortar to obtain mixed powder;
step 2, grinding the mixed powder and adding sodium hydroxide solution to obtain a mixture;
and 3, drying the mixture in an oven, grinding the dried mixture again in an agate mortar, then placing the mixture in a muffle furnace for reacting for a preset time at a preset temperature, washing and drying to obtain the iridium unit-modified cobalt spinel electrocatalytic material.
4. An iridium single site modified cobalt spinel electrocatalytic material as claimed in claim 3 wherein:
in the step 1, the mol ratio of the cobalt chloride hexahydrate to the anhydrous iridium chloride serving as a precursor is 20:1.
5. The iridium single-site modified cobalt spinel electrocatalytic material of claim 4, wherein:
in the step 1, the mass ratio of the cobalt chloride hexahydrate to the sodium chloride is 476 mg/500 mg.
6. An iridium single site modified cobalt spinel electrocatalytic material as claimed in claim 3 wherein:
the specific process of the step 2 is as follows:
placing the mixed powder in a high-energy ball milling tank for ball milling at 500rpm for 1 hour, then adding the sodium hydroxide solution, continuing placing the mixed powder in the high-energy ball milling tank for ball milling at 500rpm for 1 hour,
the concentration of the sodium hydroxide solution was 4M,
the mass volume ratio of the mixed powder to the sodium hydroxide solution is (0.9 g-1.1 g) 1mL.
7. An iridium single site modified cobalt spinel electrocatalytic material as claimed in claim 3 wherein:
wherein in step 3, the mixture is dried in the oven at a temperature of 60 ℃ for 12 hours.
8. An iridium single site modified cobalt spinel electrocatalytic material as claimed in claim 3 wherein:
in the step 3, the preset temperature is 350 ℃, the preset time is 6 hours, and the sintering gas in the muffle furnace is air.
9. An electrocatalyst, comprising:
an iridium-single-site modified cobalt spinel electrocatalytic material as claimed in any one of claims 1 to 8 and carbon powder.
10. The electrocatalyst according to claim 9, wherein:
the electrocatalyst is formed by mixing the cobalt spinel electrocatalytic material modified by iridium units and the carbon powder according to a mass ratio of 1:1.
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