CN114669314A - Preparation method of iron-based monatomic catalyst applied to oxygen reduction - Google Patents
Preparation method of iron-based monatomic catalyst applied to oxygen reduction Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000001301 oxygen Substances 0.000 title claims abstract description 26
- 230000009467 reduction Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 238000009461 vacuum packaging Methods 0.000 claims abstract description 9
- 238000002386 leaching Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 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 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 239000003708 ampul Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- MYMSECSHAJCYKM-UHFFFAOYSA-N [N].N1C=CCC1 Chemical compound [N].N1C=CCC1 MYMSECSHAJCYKM-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
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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
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract
The invention discloses a preparation method of an iron-based monatomic catalyst applied to oxygen reduction, which comprises the steps of carrying out vacuum packaging on a nitrogen-containing precursor containing zinc metal active sites and an iron source, annealing at high temperature, volatilizing the zinc atom active sites in the nitrogen-containing precursor, and substituting zinc atoms by iron atoms to form the iron-based monatomic catalyst with stronger oxygen reduction performance; compared with the traditional method, the method can effectively avoid the problem of atom agglomeration, does not need acid leaching treatment subsequently, and avoids the problem of washing off metal active sites under an acidic condition.
Description
Technical Field
The invention relates to a preparation method of an iron-based monatomic catalyst applied to oxygen reduction, belonging to the field of catalyst preparation.
Background
Most of the current methods for preparing the monatomic catalyst are to mix and load a precursor, a catalyst and a metal salt to form the monatomic catalyst under a high-temperature condition. However, the mobility of the atoms is high at high temperature, and metal agglomeration is easily formed, so that the catalyst is deactivated. So how to design the monatomic catalyst more reasonably is a current challenge.
Disclosure of Invention
Aiming at the problems of the existing method for preparing the monatomic catalyst, the invention provides the method for preparing the monatomic catalyst by the gas phase transportation method, and the method not only can successfully prepare the monatomic catalyst, but also can well avoid the problem of atom agglomeration which can be possibly generated.
The preparation method of the iron-based monatomic catalyst applied to oxygen reduction comprises the steps of carrying out vacuum packaging on a nitrogen-containing precursor containing zinc metal active sites and an iron source, annealing at high temperature, volatilizing the zinc atom active sites in the nitrogen-containing precursor, and substituting zinc atoms with iron atoms to form the iron-based monatomic catalyst with stronger oxygen reduction performance.
The nitrogen-containing precursor containing the zinc metal active site is prepared by mixing 1, 4-terephthalonitrile, zinc chloride and conductive carbon black, fully grinding, then transferring the mixture into an ampoule tube for vacuum packaging, heating the packaged mixture to 350-450 ℃ at the speed of 3 ℃/min, preserving the heat for 20h, taking out the reactant for full grinding, transferring the reactant into a tube furnace, heating to 850-950 ℃ at the speed of 3 ℃/min under the atmosphere of argon, preserving the heat for 2h, finally, carrying out acid leaching on the reactant for 6h at the temperature of 55-65 ℃ by using 0.5mol/L hydrochloric acid, sequentially washing with deionized water and tetrahydrofuran, drying to obtain covalent triazine skeleton precursor, wherein the molar ratio of the 1, 4-terephthalonitrile to the zinc chloride is 1:9-11, and the molar ratio of the 1, 4-terephthalonitrile to the conductive carbon black is 1: 9-11.
The nitrogen-containing precursor containing the zinc metal active site can also be prepared by dissolving zinc nitrate hexahydrate in methanol, then adding the solution into methanol dissolved with 2-methylimidazole, stirring for 2 hours at room temperature, centrifuging, thoroughly washing a solid with methanol, drying in vacuum, heating to 900 ℃ at the speed of 3 ℃/min under argon atmosphere, and keeping the temperature for 2 hours, wherein the molar ratio of the zinc nitrate hexahydrate to the 2-methylimidazole is 1: 7-9.
The iron source is anhydrous ferric chloride or anhydrous ferric nitrate.
The high-temperature annealing temperature is 760-960 ℃, and the annealing time is 6-10 h.
The mass ratio of the nitrogen-containing precursor containing the zinc metal active sites to the iron source is 10: 0.5-1.
The invention has the following beneficial effects:
the invention utilizes the gas phase transportation method to prepare the iron-based monatomic catalyst, and the method has the advantages that the monatomic carrier is modified to generate atom replacement; compared with the traditional method, the method can effectively avoid the problem of atom agglomeration which is possibly generated, and the subsequent acid leaching treatment is not needed, so that the problem that the formed metal active sites are possibly washed away under the acidic condition is avoided.
Drawings
FIG. 1 is a spectrum of Fe2 p;
FIG. 2 is a spectrum of N1 s;
FIG. 3 is a spectrum of C1 s;
FIG. 4 is a Zn-2P spectrum before and after capture;
FIG. 5 is a RDE effect graph of the prepared iron-based monatomic catalyst;
FIG. 6 is a comparison of the Tafel slope of an iron-based monatomic catalyst versus Pt/C in an acidic medium;
FIG. 7 shows the result of comparing the number of transferred electrons of the iron-based monatomic catalyst and Pt/C with the hydrogen peroxide yield;
FIG. 8 is a graph showing the stability results of an iron-based monatomic catalyst;
FIG. 9 is a comparison of the RDEs of catalysts prepared by annealing at different temperatures of example 2.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the above-described examples.
Example 1
1. Mixing 0.391g of 1, 4-terephthalonitrile, 4.172g of zinc chloride and 0.36g of conductive carbon black (super-p), fully grinding in a glove box, then transferring to an ampoule tube for vacuum packaging, putting the packaged mixture in a muffle furnace, heating to 400 ℃ at a rate of 3 ℃/min, preserving heat for 20h, taking out a reactant for fully grinding, transferring to a tube furnace, heating to 900 ℃ at a rate of 3 ℃/min under an argon atmosphere, preserving heat for 2h, finally, carrying out acid leaching on the reactant for 6h at a temperature of 55-65 ℃ by using 0.5mol/L hydrochloric acid, sequentially washing by using deionized water and tetrahydrofuran, and drying to obtain a covalent triazine skeleton precursor;
2. Packaging the covalent triazine skeleton precursor and anhydrous ferric chloride into a quartz tube according to the mass ratio of 10:0.5, carrying out vacuum packaging by using an oxyhydrogen welding machine, transferring the quartz tube into a muffle furnace, raising the temperature to 760 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 10 hours, carrying out acid leaching on a sample for 2 hours by using 0.01mol/L hydrochloric acid to remove ferric chloride deposited on the surface, washing the sample by using deionized water, and carrying out vacuum drying for 6 hours;
electrochemical workstation testing: pouring 5mg of dried iron-based monatomic catalyst powder into an agate mortar, adding 20 mu L of absolute ethyl alcohol to grind the catalyst for 10min, continuously dropwise adding alcohol by using a liquid-moving gun during the period to keep the sample wet, then adding 500 mu L of mixed solvent of alcohol and deionized water (the volume ratio is 3: 2), adding 20 mu L of Nafion solution and carrying out ultrasonic dispersion for 30min to obtain the iron monatomic catalyst suspension suitable for electrochemical tests.
The XPS characterization of the iron-based monatomic catalyst prepared in this example is shown in FIGS. 1-3, and after high temperature trapping, iron doping is clearly seen in the XPS characterization, and the XPS spectrum shows that Fe (2.17 at%), N (3.78 at%) and C (93.12 at%) coexist in Fe-CTF. The high resolution spectrum shows two pairs of Fe peaks, Fe respectively 2+(724.6 eV and 711.2 eV), Fe3+(729.3 eV and 715.2 eV). The N1 spectrum shows three peaks, pyrroline nitrogen (400.9 eV), pyridine nitrogen (398.2 eV) and iron-coordinated nitrogen (400.1 eV), respectively. Pyridine N has been shown to play an important role in the formation of Fe-N-C with altered local electronic structure, which can effectively improve the local electronic structure and promote the four-electron transfer during ORR. The high level of pyridine N not only facilitates the anchoring of the individual iron atoms, but also contributes to the enhancement of ORR activity. High resolution C1s spectra showed three peaks, 289.1eV, 285.7eV and 284.6eV, and conductivity of Sp2C is believed to increase ORR activity due to C-O, C-N and C-H, respectively.
The XPS spectra of zinc in the materials before and after capture in the experiment are shown in FIG. 4, and the change of the XPS spectra of Zn-2P before and after high-temperature capture can obviously observe that zinc is almost completely volatilized after high-temperature annealing and is substituted by doping of iron atoms.
FIG. 5 is an RDE performance diagram of an iron-based monatomic catalyst, which is measured by Chenhua workstation, first introducing ten minutes of oxygen into an acidic electrolyte (0.1 mol/L perchloric acid) to make the electrolyte in an oxygen-rich state, after the oxygen reduction performance of the material is tested, shutting down the oxygen, then introducing ten minutes of nitrogen into the electrolyte, and simultaneously measuring the oxygen reduction effect under the nitrogen, and subtracting the oxygen reduction effect of the nitrogen from the oxygen reduction effect of the oxygen to obtain the final oxygen reduction effect of the catalyst.
As can be observed from FIG. 5, after the high-temperature gas phase capture, the oxygen reduction performance of the catalyst is greatly improved, the initial potential reaches 0.9197V, and the half-wave potential reaches 0.7889V. Compared with a zinc monatomic catalyst (the initial potential is 0.840V, and the half-wave potential is 0.717V), the activity of the catalyst in an acid electrolyte is greatly improved.
FIG. 6 is a comparison of the Tafel slope of iron monatomic catalyst versus Pt/C in acidic media. The iron monatomic catalyst is 38mV, which is only 6mV lower than Pt/C, indicating that the catalyst has good mass transfer and transportation efficiency. FIG. 7 is a comparison of the electron transfer number of the iron monatomic catalyst compared to the hydrogen peroxide yield for Pt/C, where the iron monatomic catalyst has a transfer electron number of 4.04, comparable to Pt/C (3.98), indicating that the catalyst is in accordance with the four electron transfer mechanism, and the hydrogen peroxide yield is also comparable to Pt/C, less than 3%, and is extremely low, corresponding to the results for the Tafel slope.
FIG. 8 shows that 5000 times of cyclic voltammetry curves of the iron monatomic catalyst are measured in a voltage range of 0.6V-1.0V, after 5000 times of cycles, the catalyst is tested under the same condition for oxygen reduction, and compared with the previous test, the half-wave potential of the catalyst is only reduced by 17mV, and the good stability is shown.
Example 2:
1. this example was the same as example 1 for the preparation of the covalent triazine backbone precursor;
2. packaging a covalent triazine skeleton precursor and anhydrous ferric nitrate into a quartz tube according to the mass ratio of 10:1, performing vacuum packaging by using an oxyhydrogen welding machine, transferring the quartz tube into a muffle furnace, heating to 860 ℃ at the heating rate of 5 ℃/min, preserving heat for 10 hours, performing acid leaching on a sample by using 0.01mol/L hydrochloric acid for 2 hours to remove ferric chloride deposited on the surface, washing the sample by using deionized water, and performing vacuum drying for 6 hours;
the iron-based monatomic catalyst obtained in this example was tested for oxygen reduction in the same manner as in example 1, and the results are shown in fig. 9, where it can be seen that when the temperature is lower than 760 ℃, zinc atoms are not volatilized and iron atoms cannot be trapped. When the temperature is higher than 760 ℃, the catalyst is partially carbonized by an excessively high temperature, affecting the catalyst effect.
Example 3:
1. dissolving 10mmol of zinc nitrate hexahydrate in methanol, adding the dissolved zinc nitrate hexahydrate into 80mmol of 2-methylimidazole methanol, stirring for 2 hours at room temperature, centrifuging, thoroughly washing a solid with methanol, drying in vacuum, heating to 900 ℃ at the speed of 3 ℃/min under the argon atmosphere, and keeping the temperature for 2 hours to obtain a nitrogen-containing precursor containing a zinc metal active site;
2. packaging a nitrogen-containing precursor of a zinc metal active site and anhydrous ferric chloride into a quartz tube according to the mass ratio of 10:0.5, performing vacuum packaging by using an oxyhydrogen welding machine, transferring the quartz tube into a muffle furnace, raising the temperature to 760 ℃ at the temperature rise rate of 5 ℃/min, preserving the temperature for 10 hours, performing acid leaching on a sample for 2 hours by using 0.01mol/L hydrochloric acid to remove ferric chloride deposited on the surface, washing the sample by using deionized water, and performing vacuum drying for 6 hours to obtain the iron-based monatomic catalyst.
Claims (6)
1. A preparation method of an iron-based monatomic catalyst applied to oxygen reduction is characterized by comprising the following steps: and (2) carrying out vacuum packaging on the nitrogen-containing precursor containing the zinc metal active sites and an iron source, annealing at high temperature, volatilizing the zinc atom active sites in the nitrogen-containing precursor, and substituting zinc atoms by iron atoms to form the iron-based monatomic catalyst with stronger oxygen reduction performance.
2. The method for preparing an iron-based monatomic catalyst for oxygen reduction according to claim 1, wherein: the nitrogen-containing precursor containing zinc metal active sites is prepared by mixing 1, 4-terephthalonitrile, zinc chloride and conductive carbon black, fully grinding, then transferring the mixture into an ampoule tube for vacuum packaging, heating the packaged mixture to 350-450 ℃ at the speed of 3 ℃/min, preserving the heat for 20h, taking out the reactant for full grinding, transferring the reactant into a tube furnace, heating to 850-950 ℃ at the speed of 3 ℃/min under the atmosphere of argon, preserving the heat for 2h, finally, carrying out acid leaching on the reactant for 6h at the temperature of 55-65 ℃ by using 0.5mol/L hydrochloric acid, sequentially washing with deionized water and tetrahydrofuran, drying to obtain covalent triazine skeleton precursor, wherein the molar ratio of the 1, 4-terephthalonitrile to the zinc chloride is 1:9-11, and the molar ratio of the 1, 4-terephthalonitrile to the conductive carbon black is 1: 9-11.
3. The method of preparing an iron-based monatomic catalyst for oxygen reduction according to claim 1, wherein: the nitrogen-containing precursor containing the zinc metal active site is prepared by dissolving zinc nitrate hexahydrate in methanol, adding the solution into methanol dissolved with 2-methylimidazole, stirring for 2 hours at room temperature, centrifuging, thoroughly washing a solid with methanol, drying in vacuum, heating to 900 ℃ at the temperature of 3 ℃/min under the argon atmosphere, and keeping the temperature for 2 hours, wherein the molar ratio of the zinc nitrate hexahydrate to the 2-methylimidazole is 1: 7-9.
4. The method of preparing an iron-based monatomic catalyst for oxygen reduction according to claim 1, wherein: the iron source is anhydrous ferric chloride or anhydrous ferric nitrate.
5. The method for preparing an iron-based monatomic catalyst for oxygen reduction according to claim 1, wherein: the high-temperature annealing temperature is 760-960 ℃, and the annealing time is 6-10 h.
6. The method for preparing an iron-based monatomic catalyst for oxygen reduction according to claim 1, wherein: the mass ratio of the nitrogen-containing precursor containing the zinc metal active sites to the iron source is 10: 0.5-1.
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| US20210047741A1 (en) * | 2018-02-13 | 2021-02-18 | Gaznat Sa | Fe-N-C CATALYST, METHOD OF PREPARATION AND USES THEREOF |
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