CN114678544A - Preparation method of 3D multi-stage pore nitrogen-doped carbon-supported monatomic Fe catalyst - Google Patents
Preparation method of 3D multi-stage pore nitrogen-doped carbon-supported monatomic Fe catalyst Download PDFInfo
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—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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- 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
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Abstract
The invention provides a preparation method of a 3D multi-level pore nitrogen-doped carbon-supported monatomic Fe catalyst. The preparation method of the embodiment comprises the following steps: soaking and adsorbing a solution containing iron ions by using Polyacrylonitrile (PAN) and Polystyrene (PS) nano materials which are uniformly mixed to obtain PAN/PS-Fe; pre-oxidizing PAN/PS-Fe to obtain a pre-oxidized product OPAN/PS-Fe so as to utilize imine nitrogen formed in the pre-oxidation process of PAN to primarily anchor iron ions; soaking the OPAN/PS-Fe in a Tetrahydrofuran (THF) solution for a preset time, and then filtering and washing to remove the PS to obtain 3DHP-OPAN-Fe with a 3D hierarchical pore structure; and (3) pickling the 3DHP-OPAN-Fe, and then roasting for a preset time at 800-1000 ℃ in an inert atmosphere. The Fe in the catalyst prepared by the method is dispersed in the carbon carrier in a single atom mode, and the catalyst has extremely high electrocatalytic activity, stability and methanol resistance.
Description
Technical Field
The invention relates to the field of non-noble metal single-atom catalysts; more particularly, relates to a preparation method of a nitrogen-doped carbon-supported Fe monatomic catalyst with a 3D hierarchical pore structure.
Background
Clean, sustainable fuel cells are considered to be one of the most promising energy conversion applications. The cost of the fuel cell is mainly focused on the cathode side ORR reaction catalyst. At present, the platinum-based catalyst with excellent performance is still the ORR catalyst with the most commercial application prospect. However, noble metals are high in cost and scarce in reserves, and people are promoted to research non-noble metal catalysts which are low in cost and high in natural abundance. In this context, non-noble transition metal catalysts with nitrogen coordination (M-N-C) are ideal catalysts to replace noble metals. Among them, the monatomic M-N-C catalyst becomes a research hotspot due to the maximized atom utilization rate, uniform active center structure and clear structure-activity relationship.
The method for preparing the M-N-C monoatomic catalyst is a common method for preparing the M-N-C monoatomic catalyst by pyrolyzing a precursor mixture containing metal, nitrogen and carbon at high temperature and then pickling, but metal atoms are easy to migrate and agglomerate at high temperature to form nano particles, and although the metal particles can be removed by a pickling mode generally, the metal particles formed by high-temperature annealing are coated by a graphite carbon layer in many cases, and the graphite layer is insoluble in acid, so that the coated metal nano particles are difficult to be pickled, and therefore the carbon-coated metal nano particles and the monoatomic catalyst are often obtained as a result of the existence of the carbon-coated metal nano particles and the monoatomic catalyst at the same time.
The key point of the synthesis of the monoatomic is that the metal atom has a proper anchoring site in the carbonization process, so that the metal atom is not subjected to migration and agglomeration to generate metal particles in the high-temperature process. In the prior art, macrocyclic organic ligands such as porphyrin, phthalocyanine and the like are often used for anchoring metal in advance to obtain an M-N coordination structure, but the organic ligands have the defect of high price.
Polyacrylonitrile, due to its abundance of cyano groups, is also used as a nitrogen-containing carbon precursor to prepare nitrogen-doped ORR catalysts. However, in the prior art, the metal is compounded in by using an electrostatic spinning mode, and the obtained catalyst is not a monoatomic catalyst.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a monatomic Fe-N-C catalyst, Fe in the catalyst obtained by the preparation method is dispersed in a carbon carrier with a 3D hierarchical pore structure in a monatomic mode, and the catalyst has extremely high electrocatalytic activity, stability and methanol resistance.
In order to achieve the main purpose, the invention provides a preparation method of a nitrogen-doped carbon-supported monatomic Fe catalyst, which comprises the following steps:
soaking and adsorbing a solution containing iron ions by using Polyacrylonitrile (PAN) and Polystyrene (PS) nano materials which are uniformly mixed to obtain PAN/PS-Fe;
carrying out pre-oxidation treatment on PAN/PS-Fe to obtain a pre-oxidation product OPAN/PS-Fe so as to primarily anchor iron ions by utilizing imine nitrogen formed in the PAN in the pre-oxidation process;
soaking the OPAN/PS-Fe in a Tetrahydrofuran (THF) solution for a preset time, and then filtering and washing to remove the PS to obtain 3DHP-OPAN-Fe with a 3D hierarchical pore structure;
and (3) pickling the 3DHP-OPAN-Fe, and then roasting for a preset time at 800-1000 ℃ in an inert atmosphere.
The technical scheme has the following beneficial effects:
the method comprises the steps of anchoring Fe atoms by skillfully utilizing imine nitrogen formed during pre-oxidation of polyacrylonitrile, and removing redundant un-anchored Fe through acid washing before roasting (carbonization) at 800-1000 ℃, so that metal particles are prevented from being formed in a high-temperature roasting process, and finally a Fe monatomic catalyst is obtained; wherein Fe, which has been anchored by imine nitrogen under high temperature conditions, is finally incorporated into the carbon substrate to form Fe-NxAn active site.
The frame structure with the 3D multilevel holes is formed by removing PS after PAN pre-oxidation, and the structure is favorable for fully exposing Fe-NxActive sites, which improve the utilization rate of the active sites, thereby further improving the ORR catalytic activity.
According to a specific embodiment of the present invention, polyacrylonitrile and polystyrene nano-materials are mixed in an alcohol-water solution, and then filtered, separated and dried to obtain the uniformly mixed polyacrylonitrile and polystyrene nano-materials. Wherein, the alcohol aqueous solution can be a mixed solution of ethanol and water, and the volume ratio of the ethanol to the water can be 1: 1.
Preferably, the polyacrylonitrile and the polystyrene nano-materials are respectively added into two parts of alcohol-water solution and ultrasonically dispersed, then the two parts of alcohol-water solution are mixed, and then the mixture is filtered, separated and dried to obtain the uniformly mixed polyacrylonitrile and polystyrene nano-materials. The mixture is carried out after the ultrasonic dispersion, so that the mixture of the PAN and the PS can be more uniform, and the 3D frame structure can be obtained after the PS is removed.
According to a specific embodiment of the present invention, the mass ratio of polyacrylonitrile to polystyrene is 2:1 to 1:3, such as 2:1, 1:1 or 1:3, preferably 1: 1.
according to a specific embodiment of the present invention, the polyacrylonitrile nano material is polyacrylonitrile nanospheres, and the polystyrene nano material is polystyrene nanospheres.
According to a specific embodiment of the invention, the pre-oxidation treatment comprises roasting PAN/PS-Fe in an air environment at a temperature of 250-350 ℃ so that cyano groups in polyacrylonitrile are cyclized to obtain imine nitrogen, and coordination sites are provided for anchoring Fe.
According to one embodiment of the invention, 3DHP-OPAN-Fe is added to a sulfuric acid solution to perform the acid washing.
According to an embodiment of the invention, the solution containing iron ions is an iron nitrate solution, and the concentration of the iron nitrate solution is 0.01 mol/L-0.03 mol/L.
Preferably, before the impregnation and adsorption, the polyacrylonitrile and the polystyrene nano-materials which are uniformly mixed are subjected to vacuum degassing treatment to remove air in gaps among PAN/PS solid particles, which is more favorable for the sufficient adsorption and impregnation of iron ion solution.
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. 1 is a comparison XRD plot of the 3DHP-C-H-OPAN-Fe catalyst prepared in the examples, the 3DHP-C-OPAN-Fe catalyst prepared in comparative example 1, the 3DHP-H-C-OPAN-Fe catalyst prepared in comparative example 2, and the C-H-OPAN-Fe catalyst prepared in comparative example 3;
FIG. 2a is an SEM image of the 3DHP-C-H-OPAN-Fe catalyst prepared in the example;
FIG. 2b is a TEM image of the 3DHP-C-H-OPAN-Fe catalyst prepared in example;
FIG. 3a is an SEM image of the 3DHP-C-OPAN-Fe catalyst prepared in comparative example 1;
FIG. 3b is a TEM image of the 3DHP-C-OPAN-Fe catalyst prepared in comparative example 1;
FIG. 4a is an SEM image of the 3DHP-H-C-OPAN-Fe catalyst prepared in comparative example 2;
FIG. 4b is a TEM image of the 3DHP-H-C-OPAN-Fe catalyst prepared in comparative example 2;
FIG. 5 is an SEM photograph of the C-H-OPAN-Fe catalyst prepared in comparative example 3;
FIG. 6 is a nitrogen desorption curve of the 3DHP-C-H-OPAN-Fe catalyst prepared in the example;
FIG. 7 is a graph showing the pore size distribution of the 3DHP-C-H-OPAN-Fe catalyst prepared in the example;
FIG. 8 is a Mapping image under high resolution transmission electron microscopy of the 3DHP-C-H-OPAN-Fe catalyst prepared in example;
FIG. 9 is a STEM plot of the spherical aberration of the 3DHP-C-H-OPAN-Fe catalyst prepared in the example;
FIG. 10 is a graph comparing the Linear Sweep Voltammograms (LSV) of the 3DHP-C-H-OPAN-Fe catalyst prepared in the examples, the 3DHP-C-OPAN-Fe catalyst prepared in comparative example 1, the 3DHP-H-C-OPAN-Fe catalyst prepared in comparative example 2, and the C-H-OPAN-Fe catalyst prepared in comparative example 3;
FIG. 11 shows the respective N concentrations of the 3DHP-C-H-OPAN-Fe catalysts prepared in the examples2And O2A comparison graph of electrochemical cyclic voltammograms (C-V) under saturated conditions;
FIG. 12 is a graph comparing the cycle durability tests (LSV) for the 3DHP-C-H-OPAN-Fe catalyst and the commercial Pt/C catalyst made in the examples;
FIG. 13 is a graph comparing the chronoamperometric curves (i-t) of the methanol resistance test of the 3DHP-C-H-OPAN-Fe catalyst prepared in the examples with that of a commercial Pt/C catalyst.
Detailed Description
The embodiment of the invention provides a preparation method of a monatomic Fe-N-C catalyst, wherein Fe in the catalyst obtained by the preparation method is dispersed in a 3D hierarchical pore structure carbon carrier in a monatomic manner, and the catalyst has extremely high electrocatalytic activity, stability and methanol resistance.
The preparation method of the embodiment of the invention comprises the following steps:
mixing and dispersing Polyacrylonitrile (PAN) nanospheres and Polystyrene (PS) nanospheres in an alcohol-water mixed solution according to a mass ratio of 2: 1-1: 3, filtering and separating to obtain uniformly mixed PAN/PS filter cakes, and drying the PAN/PS filter cakes;
secondly, vacuum degassing is carried out on the dried PAN/PS filter cake, then the PAN/PS filter cake is soaked in ferric nitrate solution for adsorption, and the PAN/PS-Fe is obtained after filtration and drying; wherein the concentration of the ferric nitrate solution can be 0.01-0.03 mol/L, and is preferably 0.018 mol/L;
thirdly, roasting the PAN/PS-Fe in the air at a low temperature to obtain a pre-oxidized product OPAN/PS-Fe, wherein the purpose of the step is different from that of the pre-oxidation step in the carbon fiber synthesis, the step is to utilize the imine nitrogen formed in the pre-oxidation process of the PAN to primarily anchor iron ions, and the pre-oxidation purpose in the carbon fiber synthesis is to improve the physical properties such as the toughness of the final fiber; wherein, the roasting temperature of the pre-oxidation can be 250-350 ℃, more specifically 250-300 ℃, for example 275 ℃;
fourthly, soaking the OPAN/PS-Fe in a THF solution to remove the PS, and obtaining 3DHP-OPAN-Fe with a 3D hierarchical pore structure; wherein, the soaking time can be more than 48 hours so as to fully dissolve the template PS;
fifthly, carrying out acid washing on the 3DHP-OPAN-Fe to remove redundant un-anchored Fe, and then roasting the obtained product at high temperature in a nitrogen atmosphere for preset time to obtain 3 DHP-C-H-OPAN-Fe; wherein, 0.5mol/L dilute sulphuric acid solution can be used for acid cleaning, the acid cleaning temperature can be 80 ℃, the time can be 4-12 hours, and stirring can be carried out in the acid cleaning process; the high-temperature roasting temperature can be 800-1000 ℃, and the time can be 1-3 h.
Hereinafter, the present invention will be described in more detail based on specific examples and comparative examples.
EXAMPLE 3 preparation of DHP-C-H-OPAN-Fe catalyst
Mixing 0.2g of PAN nanospheres (average particle size of 70nm) with 20mL of ethanol aqueous solution, and ultrasonically dispersing for 2 hours; mixing 0.2g of PS nanospheres (with an average particle size of 470nm) with 20mL of ethanol aqueous solution, and ultrasonically dispersing for 2 hours; and then dripping the PAN mixed solution into the PS mixed solution, uniformly mixing by ultrasonic, filtering and separating to obtain a PAN/PS filter cake, and drying in an oven at the temperature of 80 ℃ for 12 hours.
Placing the dried PAN/PS filter cake in vacuum, degassing for 2 hours, injecting 20mL of 0.02mol/L ferric nitrate solution, soaking and adsorbing for 5 hours, filtering to obtain PAN/PS-Fe, and drying in vacuum at 60 ℃.
And (3) placing the PAN/PS-Fe into a muffle furnace, heating to 275 ℃ at the speed of 0.4 ℃/min, and preserving the temperature for 1 hour to obtain a pre-oxidized product OPAN/PS-Fe.
Soaking OPAN/PS-Fe in THF solution, stirring for 12 hr, filtering, and washing with THF to remove PS to obtain 3DHP-OPAN-Fe with inverse opal structure and 3D hierarchical pore (3DHP) structure;
the 3DHP-OPAN-Fe is used in an amount of 0.5mol/L H2SO4The solution is washed by acid for 8 hours at 80 ℃ and roasted for 2 hours at 900 ℃ in nitrogen atmosphere to obtain 3 DHP-C-H-OPAN-Fe.
Comparative example 13 preparation of DHP-C-OPAN-Fe catalyst
This comparative example differs from example 1 in that it has not been subjected to an acid wash step.
Mixing 0.2g PAN with 20mL of ethanol water solution, and carrying out ultrasonic dispersion for 2 hours; mixing 0.4g of PS with 20mL of ethanol water solution, and carrying out ultrasonic dispersion for 2 hours; and then dripping the PAN mixed solution into the PS mixed solution, uniformly mixing by ultrasonic, filtering and separating to obtain a PAN/PS filter cake, and drying in an oven at the temperature of 80 ℃ for 12 hours.
Placing the dried PAN/PS filter cake in vacuum, degassing for 2 hours, injecting 10mL of 0.02mol/L ferric nitrate solution, soaking and adsorbing for 5 hours, filtering to obtain PAN/PS-Fe, and drying in vacuum at 60 ℃.
And (3) placing the PAN/PS-Fe in a muffle furnace, heating to 275 ℃ at the speed of 0.4 ℃/min, and keeping the temperature for 1 hour to obtain a pre-oxidized product OPAN/PS-Fe.
Soaking the OPAN/PS-Fe in a THF solution, stirring for 12 hours, filtering, and washing with THF to remove PS to obtain 3DHP-OPAN-Fe with a 3D hierarchical pore structure;
3DOM-OPAN-Fe is roasted for 2 hours at 900 ℃ in a nitrogen atmosphere to obtain 3 DHP-C-OPAN-Fe.
Comparative example 23 preparation of DHP-H-C-OPAN-Fe catalyst
This comparative example differs from example 1 in that the pickling step of this comparative example is after the carbonization step.
Mixing 0.2g PAN with 20mL ethanol water solution, and carrying out ultrasonic dispersion for 2 hours; mixing 0.4g of PS with 20mL of ethanol water solution, and carrying out ultrasonic dispersion for 2 hours; and then dripping the PAN mixed solution into the PS mixed solution, uniformly mixing by ultrasonic, filtering and separating to obtain a PAN/PS filter cake, and drying in an oven at the temperature of 80 ℃ for 12 hours.
Placing the dried PAN/PS filter cake in vacuum, degassing for 2 hours, injecting 10mL of 0.02mol/L ferric nitrate solution, soaking and adsorbing for 5 hours, filtering to obtain PAN/PS-Fe, and drying in vacuum at 60 ℃.
And (3) placing the PAN/PS-Fe into a muffle furnace, heating to 275 ℃ at the speed of 0.4 ℃/min, and preserving the temperature for 1 hour to obtain a pre-oxidized product OPAN/PS-Fe.
Soaking the OPAN/PS-Fe in a THF solution, stirring for 12 hours, filtering, and washing with THF to remove PS to obtain 3DHP-OPAN-Fe with a 3D hierarchical pore structure;
roasting 3DHP-OPAN-Fe at 900 deg.C for 2 hr in nitrogen atmosphere to obtain 3DHP-C-OPAN-Fe, and adding 0.5mol/L H2SO4The solution is washed with acid at 80 ℃ for 8 hours to obtain 3 DHP-H-C-OPAN-Fe.
Comparative example 3 preparation of C-H-OPAN-Fe catalyst
This comparative example differs from example 1 in that it does not use PS spheres as a template for pore formation.
Mixing 0.2g PAN with 20mL ethanol water solution, and carrying out ultrasonic dispersion for 2 hours; adding 25mg of ferric nitrate nonahydrate, stirring and adsorbing for 2 hours, centrifuging to obtain a solid, and vacuum-drying at 60 ℃ overnight to obtain PAN-Fe.
And (3) placing the PAN-Fe into a muffle furnace, heating to 275 ℃ at the speed of 0.4 ℃/min, and preserving the temperature for 1 hour to obtain a pre-oxidized product OPAN-Fe.
OPAN-Fe with 0.5mol/L H2SO4The solution is washed by acid for 8 hours at 80 ℃ and is roasted for 2 hours at 900 ℃ in nitrogen atmosphere to obtain C-H-OPAN-Fe.
Morphology, size and phase analysis of examples and comparative examples
FIG. 1 is an XRD contrast diagram of 3DHP-C-H-OPAN-Fe catalyst prepared in example, 3DHP-C-OPAN-Fe catalyst prepared in comparative example 1, 3DHP-H-C-OPAN-Fe catalyst prepared in comparative example 2, and C-H-OPAN-Fe catalyst prepared in comparative example 3, and it can be seen that the characteristic peaks of nitrogen-doped graphitic carbon appear only at 24 ℃ and 43 ℃ in both example and comparative example 3, and there are no phase peaks of other obvious metals. The 3DHP-C-OPAN-Fe catalyst prepared in the comparative example 1 and the 3DHP-H-C-OPAN-Fe catalyst prepared in the comparative example 2 have obvious phase peaks of metallic Fe and iron carbide.
Fig. 2a and 2b are SEM and TEM images of the example, respectively, and clearly see the macropores left after the PS template is removed, while the PAN nanospheres form a framework structure of 3D ordered macropores after sintering, and no metal nanoparticles are observed in the high resolution TEM.
Fig. 3a, 3b are SEM and TEM images of comparative example 1, respectively, and comparative example 1 differs from the example in that comparative example 1 has not undergone an acid washing step, and it can be seen from the SEM that the comparative catalyst has a similar framework structure to the example, but the TEM image shows a large number of metal nanoparticles, which corresponds to the XRD result, indicating that excess unanchored iron atoms would agglomerate to form metal nanoparticles without an acid washing step.
Fig. 4a, 4b are SEM and TEM images of comparative example 2, respectively, and comparative example 2 differs from the example in that the pickling step of comparative example 2 is after carbonization and the pickling step of the example is before carbonization, and it can be seen from the SEM image that the comparative catalyst has a 3D macroporous framework structure as in the example, but the TEM image shows that the comparative catalyst still has a small amount of metal particles, which is corresponding to the XRD results, which illustrate that the difference in the pickling sequence significantly affects the phase of the final catalyst, and the pickling before carbonization is key to the successful preparation of the monoatomic Fe-N-C catalyst.
Fig. 5 is an SEM image of comparative example 3, which differs from the example in that it does not use PS spheres as a template, and it can be seen from the figure that the comparative catalyst does not have a 3D macroporous framework structure, and PAN spheres are agglomerated together into a larger-sized block after carbonization.
FIG. 6 is a nitrogen adsorption and desorption curve of the 3DHP-C-H-OPAN-Fe catalyst prepared in the example, which shows a significant hysteresis loop and is a type IV adsorption isotherm, and indicates that the catalyst is a mesoporous adsorption material.
FIG. 7 is a pore size distribution diagram of the 3DHP-C-H-OPAN-Fe catalyst prepared in the example, wherein the catalyst is a microporous/mesoporous coexisting catalyst, and the combination of SEM and TEM results can confirm that the catalyst has a macroporous, mesoporous, microporous coexisting hierarchical pore structure.
FIG. 8 is a Mapping image under a high resolution transmission electron microscope of the 3DHP-C-H-OPAN-Fe catalyst prepared in the example, from which it can be seen that the elements in the catalyst are uniformly distributed and no Fe element agglomeration occurs, which is mutually corroborated with the TEM result.
FIG. 9 is a STEM chart showing the spherical aberration of the 3DHP-C-H-OPAN-Fe catalyst prepared in example, from which it is clear that the dispersion of Fe single atom is seen, and the red circle is single atom Fe. The above results all confirm the successful synthesis of the monatomic Fe catalyst.
Testing of catalytic Performance
And (3) testing conditions: at O2Testing in saturated 0.1mol/L KOH solution by using a three-electrode system; wherein the reference electrode is an Ag/AgCl electrode, and the counter electrode is a platinum electrode. All potentials in fig. 10 to 13 are converted standard hydrogen electrode potentials.
FIG. 10 is a graph comparing the Linear Sweep Voltammograms (LSV) of the 3DHP-C-H-OPAN-Fe catalyst prepared in the examples, the 3DHP-C-OPAN-Fe catalyst prepared in comparative example 1, the 3DHP-H-C-OPAN-Fe catalyst prepared in comparative example 2, and the C-H-OPAN-Fe catalyst prepared in comparative example 3. As can be seen from fig. 10, the 3DHP-C-H-OPAN-Fe catalyst of the example has significantly higher initial potential, half-wave potential, and limiting current density than the comparative example and the commercial Pt/C catalyst.
FIG. 11 shows the respective N concentrations of the 3DHP-C-H-OPAN-Fe catalysts prepared in the examples2And O2Comparison of the electrochemical cyclic voltammogram (C-V) under saturated conditions, as is evident from this comparison, with N2The 3DHP-C-H-OPAN-Fe catalyst of the example was compared in O under saturated atmosphere2Has a particularly obvious reduction peak (0) under a saturated atmosphere83V vs RHE), which indicates that the 3DHP-C-H-OPAN-Fe catalyst has excellent ORR electrocatalytic properties.
FIG. 12 is a graph comparing the cycle durability test of the 3DHP-C-H-OPAN-Fe catalyst and the commercial Pt/C catalyst prepared in the example, wherein after 1 ten thousand CV cycles, the initial potential and half-wave potential of the 3DHP-C-H-OPAN-Fe catalyst are hardly attenuated, while the commercial Pt/C catalyst is significantly attenuated. This demonstrates that the 3DHP-C-H-OPAN-Fe catalyst has better durability than the commercial Pt/C catalyst.
FIG. 13 is a comparison of the chronoamperometric curves (i-t) of the methanol tolerance test of the 3DHP-C-H-OPAN-Fe catalyst prepared in the example with a commercial Pt/C catalyst, wherein methanol was added at 200s to test the methanol cross-over tolerance of the catalyst. As can be seen from FIG. 13, the commercial Pt/C catalyst responds particularly quickly to methanol, transitioning immediately to methanol oxidation, whereas the 3DHP-C-H-OPAN-Fe catalyst has essentially no effect on methanol oxidation, being very effective against methanol cross-effects.
A commercial Pt/C catalyst of the present invention was purchased from Johnson Matthey corporation as a comparative subject.
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 (10)
1. A preparation method of a nitrogen-doped carbon-supported monatomic Fe catalyst comprises the following steps:
soaking and adsorbing a solution containing iron ions by using Polyacrylonitrile (PAN) and Polystyrene (PS) nano materials which are uniformly mixed to obtain PAN/PS-Fe;
pre-oxidizing PAN/PS-Fe to obtain a pre-oxidized product OPAN/PS-Fe so as to utilize imine nitrogen formed in the pre-oxidation process of PAN to primarily anchor iron ions;
soaking the OPAN/PS-Fe in a Tetrahydrofuran (THF) solution for a preset time, and then filtering and washing to remove the PS to obtain 3DHP-OPAN-Fe with a 3D hierarchical pore structure;
and (3) pickling the 3DHP-OPAN-Fe, and roasting for a preset time at 800-1000 ℃ in an inert atmosphere.
2. The preparation method according to claim 1, wherein the polyacrylonitrile and the polystyrene nano-material are mixed in an alcohol-water solution, and then filtered, separated and dried to obtain the uniformly mixed polyacrylonitrile and polystyrene nano-material.
3. The preparation method according to claim 2, wherein the polyacrylonitrile and the polystyrene nano-materials are respectively added into two parts of alcohol-water solution and ultrasonically dispersed, then the two parts of alcohol-water solution are mixed, and then the mixture is filtered, separated and dried to obtain the uniformly mixed polyacrylonitrile and polystyrene nano-materials.
4. The method according to claim 2, wherein the alcohol-water solution is a mixed solution of ethanol and water.
5. The preparation method according to claim 1, wherein the mass ratio of polyacrylonitrile to polystyrene is 2: 1-1: 3.
6. The preparation method according to claim 1, wherein the polyacrylonitrile nano-material is polyacrylonitrile nanospheres, and the polystyrene nano-material is polystyrene nanospheres.
7. The preparation method of claim 1, wherein the pre-oxidation treatment comprises roasting PAN/PS-Fe in an air environment at a temperature of 250-350 ℃.
8. The method according to claim 1, wherein 3DHP-OPAN-Fe is added to a sulfuric acid solution to perform the acid washing.
9. The method according to claim 1, wherein the solution containing iron ions is a ferric nitrate solution, and the concentration of the ferric nitrate solution is 0.01 to 0.03 mol/L.
10. The preparation method of claim 1, wherein the uniformly mixed polyacrylonitrile and polystyrene nano-material is subjected to vacuum degassing treatment before the impregnation and adsorption.
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