CN111704123A - Metal nitrogen-doped carbon material, and preparation method and application thereof - Google Patents
Metal nitrogen-doped carbon material, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 18
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- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- 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
-
- B01J35/23—
-
- B01J35/33—
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/647—
-
- 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
-
- 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
- B01J37/32—Freeze drying, i.e. lyophilisation
Abstract
The application discloses a metal nitrogen-doped carbon material, a preparation method and application thereof, belongs to the technical field of preparation of nano catalysts, and aims to make possible the introduction of self-assembly for preparing a special morphology structure beneficial to catalytic reaction. Meanwhile, the metal salt and the conjugated polymer are combined by ionic bonds, so that the thermal stability of the precursor is improved, and the phenomena of metal atom migration and aggregation in the pyrolysis process are greatly inhibited. And the FeNC-NW catalyst prepared according to the strategy has catalytic activity and stability which are comparable to commercial Pt/C in oxygen reduction reaction.
Description
Technical Field
The invention belongs to the technical field of preparation of nano catalysts, and particularly relates to a metal nitrogen-doped carbon material, and a preparation method and application thereof.
Background
Metallic nitrogen doped carbon material (M-N)X/C), because the metal active site has a unique outer electronic structure, the catalyst has excellent catalytic activity and selectivity in electrochemical and chemical reactions. Has wide application in energy conversion devices and chemical synthesis, and therefore has received wide attention from researchers.
M-NXA process for preparing C material features that the carbon-base precursor is pyrolyzed at high temp to increase its electric conductivity and stability and form M-NXA catalytically active site. However, under high temperature conditions, non-metallic elements in the carbon-based precursor are prone to volatile decomposition (e.g., carbon, nitrogen), resulting in significant heat loss from the compound. And the free energy of metal atoms is increased under the high-temperature condition, so that the migration and the agglomeration of the metal atoms are accelerated, and a large number of low-activity metal clusters are formed. Resulting in low utilization of metal atoms, M-NXThe active site has low dispersion density, and the M-N is seriously reducedXActivity and stability of the/C catalyst.
Existing M-NXThe preparation process of the/C material mainly comprises the following three processes: (1) will have the original M-NXThe metal ion coordinated small molecule compound (such as phthalocyanine iron or cobalt porphyrin) of the structure is pyrolyzed to obtain M-NXAnd C, material. Under the process condition, the precursor of the micromolecule has poor thermal stability and is easy to volatilize and decompose in the pyrolysis process, so that M-N is causedXthe/C material has low catalytic activity (nat. Commun, 2 (2011) 416; J. Am. chem. Soc, 139 (2017) 1424-1427). (2) Pyrolyzing nitrogen-containing polymer and metal salt mixture to obtain M-NXAnd C, material. For example, Zelenay et al reported the preparation of Fe/Co-N by pyrolysis of a mixture of Polyaniline (PANI), iron and cobalt saltsXmaterial/C (Science, 332 (2011) 443). Although, the nitrogen-containing polymer improves the thermal stability and carbon retention of the carbon-based material to some extent. However, the metal atoms in the precursor of the metal salt/polymer mixture have aggregation phenomenon, and the aggregation of the metal atoms in the pyrolysis process is still difficult to avoid, so that the density of the active metal is reduced. And M-NXThe formation of the structure is mainly with random M-N coupling, resulting in low metal site concentration and difficulty in achieving uniform distribution of the metal sites. (3) Researchers have attempted to improve the thermal stability of small molecules by increasing their interaction with carbon-based materials. For example: in 2016, Li et al reported that iron (III) porphyrin (FeP) self-assembled on the surface of carbon black to form core/shell structure non-noble metal electrocatalysts (NPMEs) consisting of uniformly coated N-doped graphene layers (small 2016, 12, 2839-2845), and weaker intermolecular workThe problem of metal atom agglomeration cannot be effectively solved because the force is not enough to support at a higher temperature. In conclusion, the existing preparation process cannot effectively solve the problem of metal atom agglomeration in the heat treatment process.
In addition, specific M-NXThe synthesis of the/C material nanostructures is limited by the original nanostructure of the precursor, whereas few precursors with specific nanostructures have been reported. Such as nanowire-based and nanofiber-based M-NX/C, which have unique advantages, such as: faster electron and mass transport. Therefore, a low-cost and high-efficiency strategy is developed to prepare M-N with high densityXSites and unique nanostructured M-NXthe/C material is the key to achieving its high catalytic activity.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a metal nitrogen-doped carbon material, and a preparation method and application thereof.
Based on the purpose, the invention adopts the following technical scheme:
a preparation method of a metal nitrogen-doped carbon material comprises the following steps:
(1) adding hydrochloric acid and m-phenylenediamine into deionized water, and uniformly stirring at room temperature to obtain a solution A; dissolving potassium ferrocyanide in deionized water, and stirring for 10-50 minutes at room temperature in the absence of light to obtain a solution B; dissolving sodium bicarbonate and ammonium persulfate in deionized water to obtain a solution C;
(2) heating the solution A to 50-60 ℃, dropwise adding the solution B into the solution A while stirring, stirring for 2-4 h at 50-60 ℃ after dropwise adding is ended, filtering, washing the obtained solid, and dispersing the solid in deionized water to obtain a suspension D; dropwise adding the solution C into the suspension D, and stirring for 2-4 h at 15-35 ℃; filtering, washing the solid, dispersing the washed solid in deionized water, and freeze-drying;
specifically, the method comprises the following steps: the product formed at a reaction temperature of 30 ℃ to 35 ℃ is designated as Fe-PMPD-NW.
The product formed at a reaction temperature of 15 ℃ to 20 ℃ is designated as Fe-PMPD-NP.
Or adding the solution C into the solution A at the temperature of 30-35 ℃, and stirring for 2-4 h at the temperature of 30-35 ℃; filtering, washing the solid, and dispersing the washed solid in distilled water to obtain a suspension E; adding the solution B into the suspension E, stirring at room temperature for 20-40 minutes to obtain a suspension, filtering, washing the solid, dispersing the washed solid in deionized water, and freeze-drying; denoted as Fe-PMPD-Mix.
(3) And carrying out pyrolysis treatment on the freeze-dried product to obtain the metal nitrogen-doped carbon material which is respectively marked as FeNC-NW, FeNC-NP and FeNC-Mix.
Furthermore, the molar ratio of the potassium ferrocyanide to the m-phenylenediamine to the hydrochloric acid is 1:2:4, the molar ratio of the potassium ferrocyanide to the ammonium persulfate to the sodium bicarbonate is 1:2:4.4, and the freeze drying is to freeze dry the potassium ferrocyanide to the sodium bicarbonate at the temperature of minus 40 ℃ to minus 50 ℃ for more than 24 hours.
Further, the specific process of the pyrolysis treatment is as follows:
first heat treatment: under the argon atmosphere, the gas flow is 1L/min, the mixture is heated to 150 ℃ at the speed of 5 ℃/min and is kept warm for 2 h, then the mixture is heated to 600 ℃ at the heating rate of 5 ℃/min and is kept warm for 1 h, then the mixture is cooled to room temperature at the cooling rate of 5 ℃/min and is taken out, a calcined sample is soaked in concentrated hydrochloric acid solution for 5-10 h, then repeated centrifugation and washing are carried out until the aqueous solution is neutral, and centrifugation and drying are carried out;
and (3) second heat treatment: and (3) heating the product dried by the first heat treatment to 850 ℃ at the heating rate of 5 ℃/min in an ammonia atmosphere with the air flow of 1L/min, preserving the heat for 2 h, cooling to room temperature at the cooling rate of 5 ℃/min, taking out, soaking the calcined sample in a concentrated hydrochloric acid solution for 5-10 h, repeatedly centrifuging and washing until the aqueous solution is neutral, centrifuging, and freeze-drying to obtain the target product.
The metal nitrogen-doped carbon materials FeNC-NW, FeNC-NP and FeNC-Mix prepared by the preparation method.
The application of metallic nitrogen doped carbon materials FeNC-NW, FeNC-NP and FeNC-Mix as ORR catalysts.
The application firstly provides the self-assembly induced preparation of M-N from the metal ion conjugated polymer with special formXCatalyst precursor strategy. The carbon-based precursor is prefabricated in shape by a self-assembly means,the catalyst with a special advantageous nano structure is further constructed by oxidative polymerization by utilizing a special arrangement form of the self-assembled precursor for catalytic reaction. With Fe-NXThe preparation of/C is taken as an example to further prove the advantages of the strategy. Firstly, protonized m-phenylenediamine and potassium ferrocyanide are taken as structural units, and are self-assembled and arranged to form ordered ionic compound nanosheets. And further contacting an oxidant solution with the surface of the ionic compound nanosheet to perform solid-liquid reaction, and oxidizing and polymerizing the mixture by utilizing the ordered arrangement of the m-phenylenediamine and the potassium ferrocyanide monomer to form a precursor of the metal ion conjugated polymer nanowire structure. Due to the strong ionic bond between the metal ions and the nitrogen-containing amino conjugated polymer, the migration and agglomeration of metal atoms in the pyrolysis process can be effectively inhibited, and Fe-N can be realized in the high-temperature pyrolysis process4In situ transformation of (a). The characteristics show that the strategy not only can preferentially generate single metal atom catalytic active centers with high concentration and uniform distribution, but also can inhibit the formation of metal particles, and Fe-N with the form of a nanowire structureXthe/C catalyst has certain advantages in the aspects of electron transfer and material transmission. Takes electrochemical Oxygen Reduction Reaction (ORR) as model reaction, Fe-N with nanowire structureXThe half-wave potential of the/C material under acidic and alkaline conditions is 0.82V and 0.90V respectively, and the excellent ORR catalytic activity is shown. It is noted that the "self-assembly induced metal ion conjugated polymer" strategy may be to prepare other M-NXGeneral procedure for the/C material.
The invention adopts a method of inducing the metal ion conjugated polymer by self-assembly to generate the carbon-based precursor with the shape of the nanowire, and the metal group is connected with the conjugated polymer by an ionic bond to enhance the thermal stability of the precursor. Carbonizing under twice thermal decomposition to form the nano-wire material of metal nitrogen doped carbon, and forming FeN by the chemical bond coordination of iron atoms and amino groups on the conjugated polymer4And (5) structure. Fe-N4The structure is an active center, and the special electronic structure of the catalyst enables the catalyst to have better stability and excellent catalytic activity. And the nanowire structure facilitates electron transfer and mass transport in a catalytic reaction.
Compared with the prior art, the invention has the following advantages and effects.
(1) The synthesis method is simple and effective, and Fe-N can be directly obtained4The catalytic active center solves the problems of complexity and difficulty in realizing large scale in the prior art.
(2) The metal of the invention is combined with carbon base in an ionic bond mode, so that the thermal stability of the metal is improved.
(3) The metal is combined and anchored with the amino group in the conjugated polymer, so that the uniform distribution of the metal in the conjugated polymer is improved.
(4) The invention adopts a self-assembly induction mode to construct a special morphology structure which has certain advantages on the aspects of electron transmission and material transmission for catalytic reaction.
(5) The catalyst synthesized by the method has excellent performance, and the ORR catalytic activity can be compared favorably with that of noble metal Pt/C.
Drawings
FIG. 1 (a) is a flow chart of the preparation of the FeNC-NW and FeNC-NP catalysts of examples 1 and 2; (b) scanning electron micrographs of Fe-MPD-NSs prepared by examples 1 and 2, (c) of Fe-PMPD-NW prepared by example 1, (d) of Fe-PMPD-NP prepared by example 2;
FIG. 2 is a high resolution TEM image of Fe-MPD-NSs nanosheets obtained in example 1;
FIG. 3 is an SEM image of Fe-MPD-NSs nanosheets obtained in example 1;
FIG. 4 is a representation of the growth of Fe-PMPD-NW prepared in example 1, (a) an SEM image of Fe-MPD; (b) SEM image of Fe-MPD nanosheet polymerization degree 1/4; (c) SEM image of Fe-MPD nanosheet polymerization degree 1/2; (d) SEM image of Fe-MPD nanosheet polymerization degree of 1, and polymerization temperature of 35 ℃;
FIG. 5 is a SEM photograph of Fe-PMPD-NP prepared in example 2;
FIG. 6 is a transmission electron micrograph of a second heat treatment of the FeNC-NW and FeNC-Mix catalysts prepared in examples 1, 3; (a) TEM and (b) HRTEM images of the FeNC-NW before pickling; (c) TEM image of acid-washed FeNC-NW; (d) TEM and (e) HRTEM images of the FeNC-Mix before pickling; (f) acid washing a TEM image of the FeNC-Mix;
FIG. 7 is a topographical characterization of the FeNC-NW catalyst prepared in example 1. (a) SEM image of the FeNC-NW nanowires (inset is magnified image of the FeNC-NW); (b) TEM image of FeNC-NW nanowires; (c) HAADF-STEM images and corresponding EDX elemental maps of the FeNC-NW samples (Fe, deep red; N, indigo; C, bright red); (d) magnified HAADF-STEM image of FeNC-NW (isolated bright spots marked with light yellow circles are iron atoms);
FIG. 8 is a linear scan element distribution plot for the FeNC-NW catalyst prepared in example 1;
FIG. 9 is a topographical structure characterization of the FeNC-NP catalyst prepared in example 2: (a) SEM images of FeNC-NP nanoparticles (inset is an enlarged image of FeNC-NP); (b) TEM images of FeNC-NP nanoparticles; (c) HAADF-STEM images and corresponding EDX elemental maps of FeNC-NP samples (Fe, yellow; N, indigo; C, bright red); (d) amplified HAADF-STEM of FeNC-NP (isolated bright spots marked with light yellow circles are iron atoms);
FIG. 10 is a Raman spectrum of FeNC-NW, FeNC-NP, and FeNC-Mix;
FIG. 11 shows XPS spectra of FeNC-NW, FeNC-NP and FeNC-Mix: (a) XPS N1s spectra; (b) XPS Fe 2p spectroscopy;
FIG. 12 is a graph of the isotherms of FeNC-NW, FeNC-NP and FeNC-Mix, (a) nitrogen adsorption-desorption; (b) pore size distribution;
fig. 13 is a chemical structure composition further characterizing the FeNC-NW catalyst at atomic scale: (a) FeNC-NW, Fe2O3XANES spectra of the Fe K near-edge structure of the FePc and Fe foils; (b) FeNC-NW, Fe2O3Fourier Transform (FT) is carried out on XANES spectra of FePc and Fe foil near edge structures; (c) corresponding EXAFS fitting curves of the FeNC-NW in the R space;
FIG. 14 shows FeNC-NW and FeNC-Mix57Fe Mo ̈ ssbauer;
FIG. 15 is a graph of ORR performance for FeNC-NW, FeNC-NP, FeNC-Mix catalysts and reference Pt/C catalysts. (a) At O2Saturated pH =1 HClO4In solution, 5 mV s-1At a speed of 1500 rpm/min, a Linear Scanning Voltammogram (LSV) of the electrocatalyst; (b) at O2Saturated pH = 13 KOH solution at 5 mV s-1At a speed of 1500 rpm/min, a Linear Scanning Voltammogram (LSV) of the electrocatalyst;
FIG. 16 shows ORR cycle stability tests for FeNC-NW and reference Pt/C catalysts prepared in example 1 (a, b) at O2Saturated pH =1 HClO4Testing the durability in the solution; (c, d) in O2Durability test in saturated KOH (pH = 13) solution;
fig. 17 is a schematic diagram of the preparation of a metallic nitrogen-doped carbon material.
Detailed Description
In order to make the technical purpose, technical scheme and excellent effect of the present invention clearer, the technical scheme of the present invention is further described below with reference to the accompanying drawings and specific embodiments.
Material sources are as follows: potassium ferrocyanide (Aldrich); metaphenylene diamine (michelin); hydrochloric acid (shanghai chaulmoogra chemical limited); ammonium persulfate (mclin); sodium bicarbonate (mclin); deionized water (self-made 3 times water); perchloric acid (michelin); potassium hydroxide (alatin).
The purity of oxygen, argon and ammonia used in the experiment is 99.999%.
Example 1:
preparation of FeNC-NW, detailed preparation scheme FIG. 1 (a):
(1) 40 ml of 1M hydrochloric acid (HCl, 0.04 mol) and 2.16 g of M-phenylenediamine (C)6H4-(NH2)2MPD, 0.02mol) was added to 160 ml of distilled water and stirred at room temperature for 30 minutes, labeled as solution a.
4.22 g of potassium ferrocyanide (K)4[Fe(CN)6]0.01 mol) was dissolved in 200ml of distilled water and stirred at room temperature for 30 minutes without light, and labeled as solution B.
Solution a was stirred in a 55 ℃ water bath at 400 rpm and solution B was added to solution a (2 drops per second) via a constant pressure dropping funnel. The mixed solution was heated at 55 ℃ for 3 hours to form ionic compound nanosheets (Fe-MPD-NSs). The Fe-MPD-NSs suspension was filtered and washed 3 times with deionized water to remove soluble material. The Fe-MPD-NSs powder was dispersed in 400 mL deionized water to give solution C. The high resolution transmission electron micrograph of Fe-MPD-NSs is shown in FIG. 2, and the SEM image is shown in FIGS. 1 (b) and 3, from which FIG. 2, it can be seen that the crystal structure has a lattice spacing of 0.5 nm. As can be seen from FIG. 1 (b), a sheet-like structure with a smooth surface was observed, and the thickness was 380nm as can be seen from FIG. 3.
(2) 3.7 g (0.044 mol) of sodium bicarbonate and 4.56 g (0.02 mol) of ammonium persulfate were dissolved in 200ml of deionized water (solution D), and then added dropwise to solution C (2 drops per second) and stirred at 35 ℃ for 3 h to obtain a Fe-PMPD-NW polymer suspension. Fig. 4 is a diagram illustrating the growth of Fe-PMPD-NW, and it can be found that the generation of nanowires is based on the ordered arrangement of self-assembled nanosheets, and gradually generates an intercrossed nanowire network structure as the degree of polymerization increases (the degree of polymerization of the polymer is controlled by controlling the amount of ammonium persulfate added).
The Fe-PMPD-NW polymer suspension was then filtered and washed 3 times with deionized water to remove soluble material. The wet Fe-PMPD-NW powder was ultrasonically dispersed in 100 ml of deionized water, followed by freeze-drying at-45 ℃ for 24 hours to obtain a dry Fe-PMPD-NW powder.
(3) And pyrolyzing the metal ion conjugated polymer Fe-PMPD-NW twice in a tubular furnace. Under the argon atmosphere, the gas flow is 1L/min, the mixture is heated to 150 ℃ at the speed of 5 ℃/min and is kept warm for 2 h, then the mixture is heated to 600 ℃ at the heating rate of 5 ℃/min and is kept warm for 1 h, then the mixture is taken out after being cooled to room temperature at the cooling rate of 5 ℃/min, a calcined sample is soaked in concentrated hydrochloric acid solution for 8h, then repeated centrifugation and distilled water washing are carried out until the aqueous solution is neutral, centrifugation is carried out, and drying is carried out at the temperature of 60 ℃ in the air.
And (3) second heat treatment: and (3) heating the product dried by the first heat treatment to 850 ℃ at the heating rate of 5 ℃/min in an ammonia atmosphere with the air flow of 1L/min, preserving the heat for 2 h, cooling to room temperature at the cooling rate of 5 ℃/min, taking out, soaking the calcined sample in a commercially available concentrated hydrochloric acid solution for 8h, repeatedly centrifuging and washing with distilled water until the aqueous solution is neutral, centrifuging, and freeze-drying at-45 ℃ for 24h to obtain the FeNC-NW sample.
FIG. 6 (a), (b) and (c) are transmission electron micrographs of FeNC-NW, in which the agglomerate grains are small and few and in which HRTEM image shows Fe2The lattice fringes of the C nano particles are (-111); the preparation strategy of the FeNC catalyst derived from the metal nitrogen-doped carbon material can be found to have good inhibition effect on migration and agglomeration of metal ions.
FIG. 7 is SEM, TEM and EDX spectra of a sample of the FeNC-NW, from FIG. 7, it can be seen that from SEM and TEM images (a, b), the nanowire structure of the FeNC-NW with a diameter of about 80nm can be seen; (c) the EDX spectrogram shows that Fe, N and C are uniformly distributed on the surface of the nanowire; (d) high angle annular dark field scanning TEM (HAADF-STEM) further showed the catalyst to be a monoatomic catalyst, with white spots within the yellow circles being iron monoatomic.
Fig. 8 is a linear scanning element distribution diagram of the fenic-NW nanowire catalyst, and the linear scanning shows that the concentration trends of Fe, N and C are consistent, further confirming that the Fe, N and C elements are uniformly distributed on the surface of the sample.
The atomic-scale chemical structure of Fe in the fenic-NW nanowires was further investigated using extended X-ray absorption fine structure spectroscopy (EXAFS) for the fenic-NW catalyst prepared in example 1, see in particular fig. 13, with iron foil, Fe2O3And FePc as a standard sample. As can be seen from FIG. 13, (a) it can be seen that the valence of the Fe atom at the absorption edge of FeNC-NW is between Fe and Fe2+And Fe3+This is consistent with XPS results further analysis of the front end calibration curve calculated by XAENS showed that the sample has a valence state of 2.356, (b) the Fe-N peak appears at 1.56 Å, but no Fe-Fe and Fe-C peaks were detected4The cells are dispersed in the FenC-NW.
Example 2:
preparation of FeNC-NP, detailed procedure for preparation is shown in FIG. 1 (a):
(1) the Fe-MPD-NSs powder was prepared in the same manner as in step (1) of example 1.
(2) 3.7 g (0.044 mol) of sodium bicarbonate and 4.56 g (0.02 mol) of ammonium persulfate were dissolved in 200ml of deionized water (solution D), and then added to solution C (2 drops per second) to conduct polymerization, and stirred at 15 ℃ for 3 hours to obtain a suspension of Fe-PMPD-NP polymer. The Fe-PMPD-NP polymer suspension was then filtered and washed 3 times with deionized water to remove soluble material. The Fe-PMPD-NP powder was ultrasonically dispersed in 100 ml of deionized water, and freeze-dried at-45 ℃ for 24 hours to obtain a dried Fe-PMPD-NP powder, whose scanning electron micrograph is shown in FIG. 5 in detail, from which FIG. 5 it can be found that: due to low reaction kinetics, the oxidant cannot be rapidly oxidized and polymerized on the surface of the nano sheet, and therefore, the oxidant gradually falls off to form nano particles in the surface oxidation process.
(3) The Fe-PMPD-NP powder was heat-treated in the same manner as in the step (3) of example 1 to finally obtain a FeNC-NP sample, whose SEM, TEM, EDX and HAADF-STEM images are shown in detail in FIG. 9, and as can be seen from FIG. 9, SEM and TEM spectra (a, b) show that the FeNC-NP has a nanoparticle structure with a diameter of about 80 to 200 nm; (c) an EDX spectrogram shows that Fe, N and C elements are uniformly distributed on the surface of a sample; (d) the HAADF-STEM image further shows that the FeNC-NP particulate catalyst is a monoatomic catalyst, and the white spots within the yellow circles are iron monoatomic.
Example 3:
preparation of FeNC-Mix:
(1) 2.16 g of M-phenylenediamine (0.02 mol) and 40 ml of HCl solution (1M, 0.04 mol) are added to 160 ml of deionized water and stirred at room temperature for 30 minutes, labeled as solution A.
3.7 g (0.044 mol) of sodium bicarbonate and 4.56 g (0.02 mol) of ammonium persulfate were dissolved in 200ml of deionized water (solution B), and then solution B was added dropwise to solution A (2 drops per second) at 35 ℃ with stirring for 3 hours at 35 ℃ to obtain a PMPD polymer suspension. The suspension was filtered and washed 3 times with deionized water to remove soluble material to obtain PMPD powder. Ultrasonically dispersing the wet powder in100 ml of deionized water to give a solution C, 4.22 g of potassium ferrocyanide (K) are then added4[Fe(CN)6]0.01 mol) was dissolved in 200m of deionized water and stirred at room temperature for 30 minutes without light, labeled as solution D. Solution D was added dropwise to solution C (2 drops per second) and stirred at room temperature for 30 minutes to obtain a Fe/PMPD mixed suspension. The Fe/PMPD mixed suspension was filtered and washed 3 times with deionized water to remove soluble material. The wet Fe/PMPD powder was ultrasonically dispersed in 100 ml of deionized water and freeze-dried at-45 ℃ for 24 hours to obtain Fe-PMPD-Mix powder.
(2) The Fe-PMPD-Mix powder was heat-treated in the same manner as in step (3) of example 1, to finally obtain a FeNC-Mix sample. FIG. 6 (d) (e) (f) is a transmission electron micrograph of FeNC-Mix, and the agglomerate in the graph (d) is large and numerous. HRTEM image showing Fe2The lattice stripe of the C nano particle is (-101), and the preparation strategy of the FeNC catalyst derived from the metal nitrogen-doped carbon material can be found to have good inhibition effect on the migration and agglomeration of metal ions.
The Raman spectra of the FeNC-NW, FeNC-NP and FeNC-Mix prepared in examples 1, 2 and 3, showing I of the FeNC-NW, are detailed in FIG. 10D/IGThe intensity ratio of (1) to (2) was 0.74, which is lower than that of FeNC-NP (1.16) and FeNC-Mix (1.19), indicating that the FeNC-NW has a better ordered graphitic carbon structure.
X-ray photoelectron spectroscopy (XPS) of the FeNC-NWs, FeNC-NPs and FeNC-Mix prepared in examples 1, 2 and 3 is detailed in fig. 11, where (a) high resolution XPS N1s spectral analysis shows that four peaks at 398.2 eV, 399.8 eV, 401.2 eV and 403.2 eV, respectively, correspond to pyridine-N, pyrrole-N, graphite-N and graphite oxide-N, respectively; (b) the Fe 2p spectrum shows a binding energy of 711.6eV for FeNC-NW, FeNC-NP and FeNC-Mix, indicating the presence of the Fe-N structure. Fe2 +Binding energy of the species 709.6 eV, Fe2 +And Fe3 +The binding energies of (a) and (b) are 721.7 and 724 eV, respectively.
N of FeNC-NW, FeNC-NP and FeNC-Mix prepared in examples 1, 2 and 32The results of adsorption/desorption experiments to characterize BET specific surface area and pore distribution are detailed in FIG. 12, and it can be seen from FIG. 12 that (a) the specific surface area of FeNC-NW is 1193.5 m2g-1The specific surface areas of FeNC-NP and FeNC-Mix were 702.4 m2g-1And 465.5 m2g-1(ii) a (b) The FeNC-NW, the FeNC-NP and the FeNC-Mix have similar porosities, and the pore diameters are mainly distributed in the range of mesoporous structures of 2-4 nm. The FeNC-NW material derived from the polymer coordinated by metal ions has higher specific surface area and pore volume, which is more favorable for exposing active sites and faster mass transfer.
For the FeNC-NW and FeNC-Mix catalysts prepared in examples 1 and 3, 57FeM ö ssbauer spectral analysis was performed to further determine the active center structure in the FeNC catalyst, and the results are shown in detail in FIG. 14 (a) it can be seen that the FeNC-NW has good bimodal regions (D1, D2, D3) corresponding to Fe-N4Preparing components; FIG. 14 (b) is a control, except that it corresponds to Fe-N4Besides the bimodal regions of the components (D1, D2), FeNC-Mix also has a higher monomodal proportion. This indicates that there are a large amount of Fe and Fe with low catalytic activity in FeNC-Mix2C, consistent with XRD results and TEM images.
Catalytic reaction application example 1:
(1) 2mg of the catalyst of examples 1, 2 and 3 were weighed and added to 10. mu.l of Nafion solution, 0.5 ml of ethanol and 0.49 ml of deionized water, respectively, to prepare uniform slurry.
(2) 36 microliter of the slurry was applied to 0.25 cm of each2The glassy carbon electrode of (a) is formed into a uniform film. HClO at pH =14ORR electrochemical performance was tested in solution. The saturated calomel electrode is a reference electrode, and the Pt sheet is a counter electrode.
(3) 36 microliter of the slurry was applied to 0.25 cm of each2The glassy carbon electrode of (a) is formed into a uniform film. ORR electrochemical performance was tested in KOH solution at pH = 13. The saturated calomel electrode is a reference electrode, and the Pt sheet is a counter electrode.
ORR performance characterization of the FeNC-NW, FeNC-NP, FeNC-Mix and reference Pt/C catalysts prepared in examples 1, 2 and 3, see in particular FIG. 15, (a) initial potential and half-wave potential of the FeNC-NW material under acidic conditions of 0.92V and 0.82V, respectively. In contrast, the half-wave potentials of FeNC-NP and FeNC-Mix were 0.79V and 0.76V, respectively, lower than that of FeNC-NW; (b) the initial potential and half-wave potential of the FeNC-NW under alkaline conditions were 1.02V and 0.90V, respectively, comparable to Pt/C. In contrast, the half-wave potentials of FeNC-NP and FeNC-Mix were 0.87V and 0.86V, respectively, which were lower than the half-wave potential of FeNC-NW. Further, the nanowire structure has a certain promotion effect on catalytic reaction in the aspects of electron transmission and substance transmission.
The fenic-NW prepared in example 1 and the reference Pt/C catalyst were subjected to ORR cycle stability testing, as detailed in fig. 16. FIG. 16 shows that FeNC-NW has superior cycling stability under acidic and basic conditions. FIG. 17 shows M-N with nanowire structureXFe-N of/C model materialXGeneral strategy for/C preparation, the materials prepared by this strategy show efficient electrocatalytic oxygen reduction activity.
The above embodiments are only limited to the above embodiments, and any other changes, modifications, and substitutions that do not depart from the spirit and principle of the present invention are all equivalent and are included within the scope of the present invention.
Claims (6)
1. A preparation method of a metal nitrogen-doped carbon material is characterized by comprising the following steps:
(1) adding hydrochloric acid and m-phenylenediamine into deionized water, and uniformly stirring at room temperature to obtain a solution A; dissolving potassium ferrocyanide in deionized water, and stirring for 10-50 minutes at room temperature in the absence of light to obtain a solution B; dissolving sodium bicarbonate and ammonium persulfate in deionized water to obtain a solution C;
(2) heating the solution A to 50-60 ℃, dropwise adding the solution B into the solution A while stirring, stirring for 2-4 h at 50-60 ℃ after dropwise adding is ended, filtering, washing the obtained solid, and dispersing the solid in deionized water to obtain a suspension D; dropwise adding the solution C into the suspension D, and stirring for 2-4 h at 15-35 ℃; filtering, washing the solid, dispersing the washed solid in deionized water, and freeze-drying;
or adding the solution C into the solution A at the temperature of 30-35 ℃, and stirring for 2-4 h at the temperature of 30-35 ℃; filtering, washing the solid, and dispersing the washed solid in distilled water to obtain a suspension E; adding the solution B into the suspension E, stirring at room temperature for 20-40 minutes to obtain a suspension, filtering, washing the solid, dispersing the washed solid in deionized water, and freeze-drying;
(3) and carrying out pyrolysis treatment on the freeze-dried product to obtain the metal nitrogen-doped carbon material.
2. The method for preparing a metallic nitrogen-doped carbon material according to claim 1, wherein the molar ratio of the potassium ferrocyanide to the m-phenylenediamine to the hydrochloric acid is 1:2:4, the molar ratio of the potassium ferrocyanide to the ammonium persulfate to the sodium bicarbonate is 1:2:4.4, and the freeze drying is performed at-40 ℃ to-50 ℃ for 24 hours or more.
3. The method for preparing a metallic nitrogen-doped carbon material according to claim 1, wherein the pyrolysis treatment comprises the following steps:
first heat treatment: heating to 150 ℃ at a speed of 1 ℃/min under an argon atmosphere, preserving heat for 2 hours, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat for 1 hour, cooling to room temperature at a cooling rate of 5 ℃/min, taking out, soaking a calcined sample in a concentrated hydrochloric acid solution for 5-10 hours, repeatedly centrifuging and washing until the aqueous solution is neutral, centrifuging, and drying;
and (3) second heat treatment: and heating the product dried by the first heat treatment to 850 ℃ at a heating rate of 5 ℃/min in an ammonia atmosphere, preserving heat for 2 h, cooling to room temperature at a cooling rate of 5 ℃/min, taking out, soaking the calcined sample in a concentrated hydrochloric acid solution for 5-10 h, repeatedly centrifuging and washing until the aqueous solution is neutral, centrifuging, and freeze-drying to obtain the target product.
4. The method for preparing a metallic nitrogen-doped carbon material according to claim 3, wherein the freeze-drying in the pyrolysis treatment is performed at-40 ℃ to-50 ℃ for 24 hours or more.
5. A metallic nitrogen-doped carbon material produced by the production method according to any one of claims 1 to 4.
6. Use of the metallic nitrogen-doped carbon material of claim 5 as an ORR catalyst.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113877586A (en) * | 2021-10-12 | 2022-01-04 | 淮阴师范学院 | Preparation method and application of morphology-controllable hierarchical cerium-iron bimetal composite oxide |
| CN115337950A (en) * | 2022-08-23 | 2022-11-15 | 中南大学 | Preparation method of nitrogen-doped carbon-loaded high-loading transition metal monatomic catalyst |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030228972A1 (en) * | 2002-06-05 | 2003-12-11 | Birss Viola | Oxygen reduction catalyst |
| CN103326041A (en) * | 2013-06-19 | 2013-09-25 | 厦门大学 | Oxygen reduction electrocatalyst and preparation method thereof |
| CN105609793A (en) * | 2015-12-31 | 2016-05-25 | 复旦大学 | Iron-nitrogen-doped graphene porous material with dual-site catalytic oxygen reduction activity, and preparation method and application therefor |
| CN108620114A (en) * | 2018-07-06 | 2018-10-09 | 杨程飞扬 | A kind of catalyst for synthesizing 4- phenylbutanols |
| CN109103468A (en) * | 2018-08-22 | 2018-12-28 | 北京化工大学 | A kind of Fe-Mn cycle and transference charcoal oxygen reduction catalyst and its preparation method and application |
| CN110323458A (en) * | 2019-06-06 | 2019-10-11 | 山东科技大学 | It is a kind of using amine aldehyde resin as the preparation method of the oxygen reduction electro-catalyst of main precursor |
-
2020
- 2020-06-28 CN CN202010595716.6A patent/CN111704123B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030228972A1 (en) * | 2002-06-05 | 2003-12-11 | Birss Viola | Oxygen reduction catalyst |
| CN103326041A (en) * | 2013-06-19 | 2013-09-25 | 厦门大学 | Oxygen reduction electrocatalyst and preparation method thereof |
| CN105609793A (en) * | 2015-12-31 | 2016-05-25 | 复旦大学 | Iron-nitrogen-doped graphene porous material with dual-site catalytic oxygen reduction activity, and preparation method and application therefor |
| CN108620114A (en) * | 2018-07-06 | 2018-10-09 | 杨程飞扬 | A kind of catalyst for synthesizing 4- phenylbutanols |
| CN109103468A (en) * | 2018-08-22 | 2018-12-28 | 北京化工大学 | A kind of Fe-Mn cycle and transference charcoal oxygen reduction catalyst and its preparation method and application |
| CN110323458A (en) * | 2019-06-06 | 2019-10-11 | 山东科技大学 | It is a kind of using amine aldehyde resin as the preparation method of the oxygen reduction electro-catalyst of main precursor |
Non-Patent Citations (4)
| Title |
|---|
| YANSONG ZHU ET AL: "Synthesis–structure–performance correlation for poly(phenylenediamine)s/iron/carbon non-precious metal catalysts for oxygen reduction reaction", 《CATALYSIS TODAY》 * |
| YONG ZHAO ET AL: "Efficient oxygen reduction reaction electrocatalysts synthesized from an ironcoordinated aromatic polymer framework", 《J. MATER. CHEM. A》 * |
| 宋一博: "钴（铁）氮碳复合材料的制备及其催化氧还原性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 杨晓冬 等: "碳基非贵金属氧还原电催化剂的活性位结构研究进展", 《物理化学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113877586A (en) * | 2021-10-12 | 2022-01-04 | 淮阴师范学院 | Preparation method and application of morphology-controllable hierarchical cerium-iron bimetal composite oxide |
| CN113877586B (en) * | 2021-10-12 | 2023-10-31 | 淮阴师范学院 | Preparation method and application of cerium-iron bimetallic composite oxide with hierarchical structure and controllable morphology |
| CN115337950A (en) * | 2022-08-23 | 2022-11-15 | 中南大学 | Preparation method of nitrogen-doped carbon-loaded high-loading transition metal monatomic catalyst |
| CN115337950B (en) * | 2022-08-23 | 2024-01-26 | 中南大学 | Preparation method of nitrogen-doped carbon-loaded high-loading transition metal monoatomic catalyst |
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