CN112421062A - Preparation method of monoatomic iron dispersion/silver nanoparticle composite structure catalyst - Google Patents

Preparation method of monoatomic iron dispersion/silver nanoparticle composite structure catalyst Download PDF

Info

Publication number
CN112421062A
CN112421062A CN202011258092.5A CN202011258092A CN112421062A CN 112421062 A CN112421062 A CN 112421062A CN 202011258092 A CN202011258092 A CN 202011258092A CN 112421062 A CN112421062 A CN 112421062A
Authority
CN
China
Prior art keywords
iron
silver
catalyst
solution
nitrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011258092.5A
Other languages
Chinese (zh)
Inventor
曹达鹏
杨永平
杨柳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN202011258092.5A priority Critical patent/CN112421062A/en
Publication of CN112421062A publication Critical patent/CN112421062A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Catalysts (AREA)

Abstract

A preparation method of a catalyst with a monoatomic iron dispersion/silver nanoparticle composite structure is applied to oxygen reduction reaction and belongs to the technical field of electrocatalysis. The method is simple in process and convenient to operate, firstly, a ZIF-8 precursor doped with a small amount of iron is synthesized by a solvothermal method, zinc is gasified through high-temperature pyrolysis to form a nitrogen-doped porous carbon skeleton with dispersed monatomic iron (acid washing is not needed), and silver nanoparticles are loaded on the nitrogen-doped porous carbon skeleton, so that the electrocatalyst material with the composite structure of the dispersed monatomic iron and the silver nanoparticles is prepared. Through the analysis of synchrotron radiation and spherical aberration correction electron microscope, the monoatomic iron coordinates with surrounding nitrogen atoms and generates a synergistic effect with surrounding silver nanoparticles, so that the catalytic activity is further improved, and the catalyst has good oxygen reduction performance under acidic and alkaline conditions.

Description

Preparation method of monoatomic iron dispersion/silver nanoparticle composite structure catalyst
Technical Field
The invention relates to a preparation method of a catalyst for synthesizing a monoatomic iron dispersion/silver nanoparticle composite structure, which is applied to an oxygen reduction reaction and belongs to the technical field of electrocatalysis.
Background
With the large-scale use of fossil fuels, a large amount of pollutants such as waste gas and waste water are generated while the social development is promoted, and an unprecedented environmental crisis is brought. The development of new clean energy has become a common consensus in the society, and fuel cells have been increasingly spotlighted as a new energy source and have been used in some aspects.
The fuel cell is a high-efficiency energy conversion system which directly converts chemical energy in fuel into electric energy through an electrochemical process without direct combustion, and has the advantages of high power generation efficiency, low noise, no pollution, real realization of zero emission and the like. At present, fuel cells have been commercialized primarily in some fields, and are beginning to play an important role. The fuel cell mainly has the reaction action of the anode and the cathode, and compared with the Hydrogen Oxidation Reaction (HOR) reaction generated at the anode, the Oxygen Reduction Reaction (ORR) reaction generated at the cathode leads to higher overpotential due to the slow dynamic process, thus seriously hindering the improvement of the overall efficiency of the fuel cell. The development of the efficient and stable oxygen reduction catalyst for reducing the energy barrier of the oxygen reduction reaction, accelerating the reaction rate and improving the energy conversion efficiency has important significance.
Currently, the mainstream reaction mechanism model of oxygen reduction reaction considers that the process has two paths: one is 4 electrons directly produce water; one is a path in which 2 electrons generate hydrogen peroxide and are regenerated into water. But intermediate H in the 2-electron process2O2Can cause problems with degradation of the catalyst and corrosion of the electrode material, and therefore the ideal oxygen reduction reaction path should be a perfect reaction in a 4 electron process. The Pt/C catalyst is commonly used for oxygen reduction reaction at present, the catalytic performance is best, but the large-scale commercial application of the Pt/C is limited due to the expensive price and high loading capacity of Pt noble metal, and in addition, the Pt-based catalyst has the problems of poor methanol resistance, easy aggregation, serious leaching and the like. Therefore, there is an urgent need for the development of low-cost, high-activity metal catalysts.
At present, the research on the oxygen reduction reaction catalyst mainly focuses on two aspects, namely, the dosage of Pt noble metal is reduced, and the catalyst cost is reduced by adopting methods of forming Pt-based alloy and the like; secondly, a novel non-noble metal catalyst is developed, mainly comprising transition metals such as Fe, Co and the like, wherein a nitrogen element doped transition metal single-atom catalyst (M-N-C structure) becomes the most promising non-noble metal catalyst. The single atom form enables the metal active center to achieve the maximum atom utilization rate and the load capacity is lower. However, the actual catalytic performance of the catalyst is often different from that of the noble metal catalyst. The invention provides a novel catalyst which introduces another metal particle on the basis of monoatomic dispersion, further improves the catalytic performance through the synergistic action between the monoatomic particles, and has excellent performance under acidic and alkaline conditions.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method of the electrocatalyst with the monatomic iron dispersion/silver nanoparticle composite structure is provided aiming at the development current situation of the oxygen reduction catalyst of the fuel cell, and the electrocatalyst shows better oxygen reduction catalytic performance under acidic and alkaline conditions.
The technical scheme provided by the invention for solving the technical problems is as follows:
a catalyst with a monatomic iron dispersion/silver nanoparticle composite structure is characterized by being a nitrogen-doped iron-silver-carbon composite porous material, silver being in a nanoparticle shape, and iron being uniformly distributed in the nitrogen-doped porous carbon material in a monatomic dispersion state.
A preparation method of a monatomic iron dispersion/silver nanoparticle composite structure catalyst adopts a MOFs derivation method to obtain the monatomic iron dispersion/silver nanoparticle composite structure catalyst with a synergistic effect, and comprises the following steps:
(1) firstly, in-situ doping ferric acetylacetonate during ZIF-8 synthesis by utilizing a solvothermal method to obtain a ZIF-8 precursor doped with a small amount of ferric acetylacetonate, and gasifying zinc through high-temperature pyrolysis to form monoatomic iron-dispersed nitrogen-doped porous carbon skeleton Fe-N/C black powder;
(2) adding deionized water into Fe-N/C, weighing a certain amount of silver nitrate solid into the solution, adding an absolute ethyl alcohol solution into the solution, ultrasonically dispersing the mixed solution at room temperature, and stirring for 1-10 hours; centrifuging the solution, washing the solution by using absolute ethyl alcohol, and carrying out vacuum drying at 50-100 ℃ overnight;
(3) grinding the black powder dried in the step (2), placing the ground black powder into a porcelain ark, and placing the porcelain ark into a tube furnace in an inert atmosphereHigh-temperature carbonization is carried out to obtain the composite material Ag with the monoatomic iron dispersion/silver nano-particle composite structureNPs@Fe-N/C。
Further, the molar ratio of the ferric acetylacetonate to the zinc nitrate hexahydrate added in the preparation of the ferric acetylacetonate doped ZIF-8 in the step (1) is 0.005:1 to 0.1:1, preferably 0.025: 1.
And (2) carrying out high-temperature pyrolysis on the iron acetylacetonate doped ZIF-8 at 900-1100 ℃ for 1-10 h, preferably 910 ℃ for 3 h.
And (3) adding deionized water and absolute ethyl alcohol in a volume ratio of 1: 1-1: 50 in the step (2). The molar ratio of the ferric acetylacetonate added during the preparation of the iron-doped ZIF-8 to the silver nitrate added during the loading of the silver particles is 1: 0.1-1: 10, preferably 1: 1.
Preferably, when the black powder in the step (3) is carbonized in a tube furnace, inert gas is introduced for 1-10 hours at room temperature, then the temperature is raised to 200-700 ℃ at the speed of 1-20 ℃/min, the temperature is maintained for 1-10 hours, then the temperature is raised to 700-1200 ℃ at the speed of 1-20 ℃/min, the temperature is maintained for 1-10 hours, and the black powder is naturally cooled to the room temperature.
A series of characteristics such as a scanning electron microscope, a transmission electron microscope, a spherical aberration correction electron microscope, synchrotron radiation, an X-ray diffraction spectrum, an X-ray photoelectron spectrum, a Raman spectrum, elemental analysis, BET (BET) and pore size analysis prove that the prepared material is the nitrogen-doped porous carbon material compounded by the monoatomic iron dispersion/silver nanoparticles.
The invention has the following beneficial effects:
1) the invention provides a preparation method of an oxygen reduction electrocatalyst with a monatomic iron dispersion/silver nanoparticle composite structure based on ZIF-8 synthesis, which is characterized in that a ZIF-8 precursor doped with a small amount of iron is synthesized by a solvothermal method, zinc is gasified through high-temperature pyrolysis to form a monatomic iron dispersion nitrogen-doped porous carbon skeleton (acid washing is not needed), and silver nanoparticles are loaded on the basis to prepare the electrocatalyst material with the monatomic iron dispersion/silver nanoparticle composite structure. Through the analysis of synchrotron radiation and spherical aberration correction electron microscope, the monoatomic iron coordinates with surrounding nitrogen atoms and generates synergistic action with surrounding silver nanoparticles, so that the silver nanoparticles have good oxygen reduction activity under acidic and alkaline conditions.
2) Compared with the existing catalyst, the catalyst prepared by the method further improves the oxygen reduction catalytic activity through the synergistic effect between the iron monoatomic atom and the silver nano-particles compared with a single pure iron monoatomic atom or silver nano-particle catalyst, the half-wave potential under the alkaline condition is far higher than that of a commercial Pt/C catalyst, and the half-wave potential under the acidic condition is closer to that of the commercial Pt/C catalyst.
3) The preparation process of the invention does not need acid washing, avoids using toxic reagents and complex synthesis process, and the synthesis method is simple and convenient. The nitrogen-doped porous carbon skeleton derived from ZIF-8 high-temperature pyrolysis has a hierarchical porous structure and a high specific surface area, and is beneficial to reaction mass transfer and charge transfer, and the catalytic performance of the catalyst is improved by more active sites.
4) The mutually synergistic composite structure between the monoatomic particles and the nano particles, which is disclosed by the invention, also provides some new ideas for the development of oxygen reduction catalysts.
Drawings
Fig. 1 is a scanning electron microscope photograph of a single atomic iron dispersed/silver nanoparticle composite structured catalyst in example 1.
Fig. 2 is a transmission electron microscope photograph showing a spherical aberration correction of the single atomic iron dispersed/silver nanoparticle composite structured catalyst in example 1.
Fig. 3 is an element distribution diagram of a single atomic iron dispersed/silver nanoparticle composite structured catalyst in example 1.
Fig. 4 is an X-ray diffraction spectrum of a single atomic iron dispersed/silver nanoparticle composite structured catalyst in example 1.
Fig. 5 is a transmission electron micrograph of a monoatomic iron-dispersed nitrogen-doped porous carbon catalyst of example 2.
Fig. 6 is an X-ray diffraction spectrum of a monoatomic iron-dispersed nitrogen-doped porous carbon catalyst of example 2.
Fig. 7 is a transmission electron microscope photograph of the nitrogen-doped porous carbon catalyst in which silver nanoparticles are dispersed in example 3.
Fig. 8 is an X-ray diffraction spectrum of the nitrogen-doped porous carbon catalyst in which silver nanoparticles are dispersed in example 3.
Fig. 9 is an X-ray diffraction spectrum of the iron nanoparticle dispersed/silver nanoparticle composite structured catalyst in example 4.
Fig. 10 is a comparison graph of polarization curves LSV (at basic 0.1M potassium hydroxide) for the monatomic iron-dispersed/silver-nanoparticle composite structured catalyst of example 1, the monatomic iron-dispersed nitrogen-doped porous carbon catalyst of example 2, the silver-nanoparticle dispersed nitrogen-doped porous carbon catalyst of example 3, the iron-nanoparticle dispersed/silver-nanoparticle composite structured catalyst of example 4, and commercial Pt/C.
Fig. 11 is a comparison graph of polarization curves LSV (in acidic 0.5M sulfuric acid) for the monatomic iron-dispersed/silver-nanoparticle composite structured catalyst of example 1, the monatomic iron-dispersed nitrogen-doped porous carbon catalyst of example 2, the silver-nanoparticle dispersed nitrogen-doped porous carbon catalyst of example 3, the iron-nanoparticle dispersed/silver-nanoparticle composite structured catalyst of example 4, and commercial Pt/C.
Detailed Description
The technical solutions of the present invention will be further described in detail below with reference to the embodiments and the drawings, but the present invention is not limited to the following embodiments.
The experimental drugs were commercially available from the national pharmaceutical group (Beijing chemical plant, Allantin reagent, Michael reagent, Beijing Yinuoka science and technology Co., Ltd.) and were not further purified.
Example 1:
preparation method of monoatomic iron dispersion/silver nanoparticle composite structure catalyst
1) 1.19g Zn (NO) are weighed out3)2·6H2Dissolving O in 60ml of anhydrous methanol solution, adding 35.3mg of ferric acetylacetonate, and stirring at room temperature for 30min to uniformly mix the solution; weighing 1.314g of 2-methylimidazole, dissolving in 30ml of anhydrous methanol solution, and carrying out ultrasonic treatment for 20min to obtain a clear solution; adding 2-methylimidazole solution to Zn (NO)3)2·6H2The mixture was stirred at room temperature for 4 hours in O solution. (iron acetylacetonate with Zn (NO)3)2·6H2O molar ratio of 0.025:1)
2) Transferring the solution obtained in the step (1) to a hydro-thermal synthesis reaction kettle, and keeping the solution at 120 ℃ for 6 hours; and after the reaction kettle is cooled, centrifuging the solution (10000r/min,6min), washing with anhydrous methanol and DMF solution, collecting, and placing in a vacuum drying oven for vacuum drying overnight at 70 ℃ to obtain a faint yellow Fe-doped ZIF-8 precursor.
3) Grinding the product obtained in the step (2), placing the ground product into a porcelain ark, placing the porcelain ark into a tube furnace for carbonization, and introducing N at room temperature2And (3) 1h, heating to 910 ℃ at the speed of 5 ℃/min, keeping for 3h, naturally cooling to room temperature, and grinding the carbonized black solid into powder to obtain the nitrogen-doped porous carbon skeleton Fe-N/C with the monoatomic iron distribution.
4) Adding 10ml of deionized water into the Fe-N/C obtained in the step (3), weighing 17mg of silver nitrate solid into the solution, adding 20ml of absolute ethanol solution into the solution, ultrasonically dispersing the mixed solution at room temperature for 1 hour, and then stirring for 2 hours; the solution was centrifuged (8000r/min,6min), washed with absolute ethanol, collected, and vacuum dried in a vacuum oven at 70 ℃ overnight. (molar ratio of iron acetylacetonate to silver nitrate 1:1)
5) Grinding the black powder obtained in the step (4), putting the ground black powder into a porcelain ark, putting the porcelain ark into a tube furnace for carbonization, and introducing N at room temperature2Heating to 600 deg.C at a rate of 10 deg.C/min for 2h, heating to 800 deg.C at a rate of 10 deg.C/min for 2h, and naturally cooling to room temperature to obtain composite Ag material with monoatomic iron dispersion/silver nanoparticle structureNPs@Fe-N/C(Fe:Ag＝1:1)。
Example 2:
preparation method of nitrogen-doped porous carbon catalyst with dispersed monoatomic iron
1) 1.19g Zn (NO) are weighed out3)2·6H2Dissolving O in 60ml of anhydrous methanol solution, adding 35.3mg of ferric acetylacetonate, and stirring at room temperature for 30min to uniformly mix the solution; weighing 1.314g of 2-methylimidazole, dissolving in 30ml of anhydrous methanol solution, and carrying out ultrasonic treatment for 20min to obtain a clear solution; adding 2-methylimidazole solution to Zn (NO)3)2·6H2In O solutionStirred at room temperature for 4 h. (iron acetylacetonate with Zn (NO)3)2·6H2O molar ratio of 0.025:1)
2) Transferring the solution obtained in the step (1) to a hydro-thermal synthesis reaction kettle, and keeping the solution at 120 ℃ for 6 hours; and after the reaction kettle is cooled, centrifuging the solution (10000r/min,6min), washing with anhydrous methanol and DMF solution, collecting, and placing in a vacuum drying oven for vacuum drying overnight at 70 ℃ to obtain a faint yellow Fe-doped ZIF-8 precursor.
3) Grinding the product obtained in the step (2), placing the ground product into a porcelain ark, placing the porcelain ark into a tube furnace for carbonization, and introducing N at room temperature2And (3) 1h, heating to 910 ℃ at the speed of 5 ℃/min, keeping for 3h, naturally cooling to room temperature, and grinding the carbonized black solid into powder to obtain the nitrogen-doped porous carbon skeleton Fe-N/C with the monoatomic iron distribution.
Example 3:
preparation method of nitrogen-doped porous carbon catalyst with dispersed silver nanoparticles
1) 1.19g Zn (NO) are weighed out3)2·6H2Dissolving O in 60ml of anhydrous methanol solution, and stirring at room temperature for 30min to uniformly mix the solution; weighing 1.314g of 2-methylimidazole, dissolving in 30ml of anhydrous methanol solution, and carrying out ultrasonic treatment for 20min to obtain a clear solution; adding 2-methylimidazole solution to Zn (NO)3)2·6H2The mixture was stirred at room temperature for 4 hours in O solution.
2) Transferring the solution obtained in the step (1) to a hydro-thermal synthesis reaction kettle, and keeping the solution at 120 ℃ for 6 hours; and after the reaction kettle is cooled, centrifuging the solution (10000r/min,6min), washing with anhydrous methanol and DMF solution, collecting, and placing in a vacuum drying oven for vacuum drying overnight at 70 ℃ to obtain a white ZIF-8 precursor.
3) Grinding the product obtained in the step (2), placing the ground product into a porcelain ark, placing the porcelain ark into a tube furnace for carbonization, and introducing N at room temperature2And (3) 1h, heating to 910 ℃ at the speed of 5 ℃/min, keeping for 3h, naturally cooling to room temperature, and grinding the carbonized black solid into powder to obtain the N/C of the nitrogen-doped porous carbon skeleton.
4) Adding 10ml of deionized water into the N/C obtained in the step (3), weighing 17mg of silver nitrate solid into the solution, adding 20ml of absolute ethyl alcohol solution into the solution, ultrasonically dispersing the mixed solution at room temperature for 1 hour, and then stirring for 2 hours; the solution was centrifuged (8000r/min,6min), washed with absolute ethanol, collected, and vacuum dried in a vacuum oven at 70 ℃ overnight.
5) Grinding the black powder obtained in the step (4), putting the ground black powder into a porcelain ark, putting the porcelain ark into a tube furnace for carbonization, and introducing N at room temperature2Heating to 600 ℃ at the speed of 10 ℃/min for 2h, heating to 800 ℃ at the speed of 10 ℃/min for 2h, naturally cooling to room temperature to obtain the nitrogen-doped porous carbon material Ag with dispersed silver nanoparticlesNPs-N/C。
Example 4:
preparation method of iron nanoparticle dispersed/silver nanoparticle composite structure catalyst
1) 1.19g Zn (NO) are weighed out3)2·6H2Dissolving O in 60ml of anhydrous methanol solution, adding 70.6mg of ferric acetylacetonate, and stirring at room temperature for 30min to uniformly mix the solution; weighing 1.314g of 2-methylimidazole, dissolving in 30ml of anhydrous methanol solution, and carrying out ultrasonic treatment for 20min to obtain a clear solution; adding 2-methylimidazole solution to Zn (NO)3)2·6H2The mixture was stirred at room temperature for 4 hours in O solution. (iron acetylacetonate with Zn (NO)3)2·6H2The molar ratio of O is 0.05:1)
2) Transferring the solution obtained in the step (1) to a hydro-thermal synthesis reaction kettle, and keeping the solution at 120 ℃ for 6 hours; and after the reaction kettle is cooled, centrifuging the solution (10000r/min,6min), washing with anhydrous methanol and DMF solution, collecting, and placing in a vacuum drying oven for vacuum drying overnight at 70 ℃ to obtain the yellow Fe-doped ZIF-8 precursor.
3) Grinding the product obtained in the step (2), placing the ground product into a porcelain ark, placing the porcelain ark into a tube furnace for carbonization, and introducing N at room temperature2And (3) 1h, heating to 910 ℃ at the speed of 5 ℃/min, keeping for 3h, naturally cooling to room temperature, and grinding the carbonized black solid into powder to obtain the Fe-containing nitrogen-doped porous carbon skeleton.
4) Adding 10ml of deionized water into the Fe-containing nitrogen-doped porous carbon skeleton obtained in the step (3), weighing 17mg of silver nitrate solid into the solution, adding 20ml of absolute ethanol solution into the solution, ultrasonically dispersing the mixed solution at room temperature for 1 hour, and then stirring for 2 hours; the solution was centrifuged (8000r/min,6min), washed with absolute ethanol, collected, and vacuum dried in a vacuum oven at 70 ℃ overnight. (molar ratio of iron acetylacetonate to silver nitrate 2:1)
5) Grinding the black powder obtained in the step (4), putting the ground black powder into a porcelain ark, putting the porcelain ark into a tube furnace for carbonization, and introducing N at room temperature2Heating to 600 deg.C at a rate of 10 deg.C/min for 2h, heating to 800 deg.C at a rate of 10 deg.C/min for 2h, and naturally cooling to room temperature to obtain Ag-Fe/Ag nanoparticles composite structure materialNPs@FeNPs-N/C(Fe：Ag＝2:1)。
The above-described embodiments are merely examples provided for clearly illustrating the present invention and should not be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the scope of the invention as defined by the independent claims are intended to be embraced therein.
Fig. 1 is a scanning electron microscope photograph of the catalyst with the monatomic iron dispersion/silver nanoparticle composite structure of example 1, and it can be seen from the photograph that the catalyst is distributed in a polyhedral structure, the size is basically consistent, and the distribution is uniform.
In fig. 2, a spherical aberration correction electron microscope photograph of the catalyst with the monatomic iron dispersion/silver nanoparticle composite structure of example 1 shows that particles and monatomic atoms coexist, and by measuring lattice fringes and combining other characteristics, the particles are determined to be silver nanoparticles, and iron is distributed in the form of monatomic atoms (small bright spots in the figure).
The elemental distribution of the catalyst of example 1 in fig. 3, which is a composite structure of monoatomic iron dispersion/silver nanoparticle, shows that C, N elements are uniformly distributed, the particles are composed of Ag element, and Fe element is distributed in the vicinity of Ag particles.
In the X-ray diffraction spectrum of the catalyst with the monatomic iron dispersion/silver nanoparticle composite structure of example 1 in fig. 4, it can be seen that there is a distinct silver characteristic peak and no iron characteristic peak, indicating that silver nanoparticles are present and iron may be present in a monatomic form, which is consistent with the analysis results of the spherical aberration electron microscope and other characterizations in fig. 2.
A transmission electron micrograph of the monatomic iron-dispersed nitrogen-doped porous carbon catalyst of example 2 in fig. 5 shows that no significant particles are present.
The X-ray diffraction spectrum of the monoatomic iron-dispersed nitrogen-doped porous carbon catalyst of example 2 in fig. 6 shows that there is no characteristic peak of iron, and iron is not formed into particles, which is consistent with the result that no particles are seen in fig. 5.
In fig. 7, a transmission electron micrograph of the nitrogen-doped porous carbon catalyst in which silver nanoparticles are dispersed in example 3 shows that the particles are clearly present.
The X-ray diffraction spectrum of the nitrogen-doped porous carbon catalyst with dispersed silver nanoparticles of example 3 in fig. 8 shows a distinct silver characteristic peak indicating the presence of silver nanoparticles, which is consistent with the results for the particles seen in fig. 7.
In the X-ray diffraction spectrum of the iron nanoparticle dispersed/silver nanoparticle composite catalyst in example 4 of fig. 9, it can be seen that there are distinct silver characteristic peaks, and some Fe is present3O4、Fe3C, indicating the presence of elemental silver nanoparticles and some iron nanoparticles.
FIG. 10 is a comparison graph of polarization curves LSV (at 0.1M KOH in alkalinity) for the catalyst with a monoatomic iron-dispersed/silver-nanoparticle composite structure of example 1, the nitrogen-doped porous carbon catalyst with a monoatomic iron-dispersed of example 2, the nitrogen-doped porous carbon catalyst with a silver-nanoparticle dispersed of example 3, the iron-nanoparticle dispersed/silver-nanoparticle composite structure of example 4, and commercial Pt/CNPsThe half-wave potential of @ Fe-N/C reached 0.89mV, which is about 40mV higher than that of commercial Pt/C catalysts, vs. Fe-N/C, AgNPs-N/C and AgNPs@FeNPsthe-N/C is improved.
FIG. 11 is a comparison graph of polarization curves LSV (in 0.5M sulfuric acid) of the monoatomic iron-dispersed/silver-nanoparticle composite structure catalyst in example 1, the monoatomic iron-dispersed nitrogen-doped porous carbon catalyst in example 2, the silver-nanoparticle-dispersed nitrogen-doped porous carbon catalyst in example 3, the iron-nanoparticle-dispersed/silver-nanoparticle composite structure catalyst in example 4, and commercial Pt/CNPs@ Fe-N/C catalytic activity is higher than that of Fe-N/C, AgNPs-N/C and AgNPs@FeNPsthe-N/C was increased by about 25mV compared to the half-wave potential of Fe-N/C, which is closer to that of commercial Pt/C catalysts.

Claims (8)

1. A catalyst with a monatomic iron dispersion/silver nanoparticle composite structure is characterized by being a nitrogen-doped iron-silver-carbon composite porous material, silver being in a nanoparticle shape, and iron being uniformly distributed in the nitrogen-doped porous carbon material in a monatomic dispersion state.
2. A monatomic iron dispersion/silver nanoparticle composite structured catalyst as set forth in claim 1, wherein the monatomic iron is coordinated to the surrounding nitrogen atoms and synergistically interacts with the surrounding silver nanoparticles.
3. A method for preparing a monatomic iron-dispersed/silver nanoparticle composite catalyst of claim 1, which comprises the steps of:
(1) firstly, in-situ doping ferric acetylacetonate during ZIF-8 synthesis by utilizing a solvothermal method to obtain a ZIF-8 precursor doped with a small amount of ferric acetylacetonate, and gasifying zinc through high-temperature pyrolysis to form monoatomic iron-dispersed nitrogen-doped porous carbon skeleton Fe-N/C black powder;
(2) adding deionized water into Fe-N/C, weighing a certain amount of silver nitrate solid into the solution, adding an absolute ethyl alcohol solution into the solution, ultrasonically dispersing the mixed solution at room temperature, and stirring for 1-10 hours; centrifuging the solution, washing the solution by using absolute ethyl alcohol, and carrying out vacuum drying at 50-100 ℃ overnight;
(3) the step (A) is2) Grinding the dried black powder, placing the ground black powder into a porcelain ark, and putting the porcelain ark into a tube furnace to carry out high-temperature carbonization in an inert atmosphere to obtain the monoatomic iron dispersion/silver nanoparticle composite structure material AgNPs@Fe-N/C。
4. The method according to claim 3, wherein the molar ratio of the iron acetylacetonate to the zinc nitrate hexahydrate added in the step (1) of preparing the iron acetylacetonate doped ZIF-8 is 0.005:1 to 0.1:1, preferably 0.025: 1. And (2) carrying out high-temperature pyrolysis on the iron acetylacetonate doped ZIF-8 at 900-1100 ℃ for 1-10 h, preferably 910 ℃ for 3 h.
5. The method according to claim 3, wherein the volume ratio of the deionized water to the absolute ethyl alcohol added in the step (2) is 1:1 to 1: 50.
6. A process according to claim 3, characterized in that the molar ratio of iron acetylacetonate to silver nitrate is from 1:0.1 to 1:10, preferably 1: 1.
7. The method according to claim 3, wherein in the step (3), when the black powder is carbonized in the tube furnace, inert gas is introduced at room temperature for 1-10 h, the temperature is raised to 200-700 ℃ at the rate of 1-20 ℃/min and is maintained for 1-10 h, then the temperature is raised to 700-1200 ℃ at the rate of 1-20 ℃/min and is maintained for 1-10 h, and the black powder is naturally cooled to room temperature.
8. Use of a monatomic iron-dispersed/silver nanoparticle composite catalyst in accordance with claim 1 or 2, which is used for an oxygen reduction electrocatalytic reaction under acidic-basic conditions.
CN202011258092.5A 2020-11-11 2020-11-11 Preparation method of monoatomic iron dispersion/silver nanoparticle composite structure catalyst Pending CN112421062A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011258092.5A CN112421062A (en) 2020-11-11 2020-11-11 Preparation method of monoatomic iron dispersion/silver nanoparticle composite structure catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011258092.5A CN112421062A (en) 2020-11-11 2020-11-11 Preparation method of monoatomic iron dispersion/silver nanoparticle composite structure catalyst

Publications (1)

Publication Number Publication Date
CN112421062A true CN112421062A (en) 2021-02-26

Family

ID=74781106

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011258092.5A Pending CN112421062A (en) 2020-11-11 2020-11-11 Preparation method of monoatomic iron dispersion/silver nanoparticle composite structure catalyst

Country Status (1)

Country Link
CN (1) CN112421062A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113477270A (en) * 2021-07-08 2021-10-08 合肥工业大学 Preparation method of copper-iron bimetal confined nitrogen doped carbon nanotube composite material
CN114635152A (en) * 2022-03-10 2022-06-17 浙江大学衢州研究院 Preparation method and application of monoatomic dispersion carbon-based catalyst
CN114709436A (en) * 2022-03-02 2022-07-05 北京化工大学 Has Fe2Preparation and application of oxygen evolution/hydrogen evolution/oxygen reduction electrocatalyst with P/Co nano-particle synergistic effect
CN114976069A (en) * 2022-06-23 2022-08-30 香港科技大学深圳研究院 Preparation method and application of zeolite-like imidazole ester framework/graphene catalyst

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106981670A (en) * 2017-04-13 2017-07-25 湖南工业大学 A kind of hydrogen reduction composite catalyst and its preparation method and application
CN107978763A (en) * 2017-11-23 2018-05-01 华南理工大学 A kind of silver-iron-nitrogen-carbon oxygen reduction catalyst for fuel cell and preparation method and application
CN108232212A (en) * 2018-03-26 2018-06-29 济南大学 A kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst and preparation method and application
CN109841854A (en) * 2017-11-29 2019-06-04 中国科学院大连化学物理研究所 A kind of nitrogen-doped carbon-supported antozone reducing catalyst and preparation method thereof
CN109888222A (en) * 2019-02-26 2019-06-14 淮安新能源材料技术研究院 A kind of N doping porous carbon and preparation method thereof of silver nano-grain package
CN110280288A (en) * 2019-07-04 2019-09-27 山西师范大学 The preparation method of bifunctional catalyst is precipitated in a kind of nitrogen co-doped carbon material hydrogen reduction of novel transition metal -/oxygen
CN111769297A (en) * 2020-07-17 2020-10-13 郑州佛光发电设备有限公司 Cathode catalyst of aluminum-air battery and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106981670A (en) * 2017-04-13 2017-07-25 湖南工业大学 A kind of hydrogen reduction composite catalyst and its preparation method and application
CN107978763A (en) * 2017-11-23 2018-05-01 华南理工大学 A kind of silver-iron-nitrogen-carbon oxygen reduction catalyst for fuel cell and preparation method and application
CN109841854A (en) * 2017-11-29 2019-06-04 中国科学院大连化学物理研究所 A kind of nitrogen-doped carbon-supported antozone reducing catalyst and preparation method thereof
CN108232212A (en) * 2018-03-26 2018-06-29 济南大学 A kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst and preparation method and application
CN109888222A (en) * 2019-02-26 2019-06-14 淮安新能源材料技术研究院 A kind of N doping porous carbon and preparation method thereof of silver nano-grain package
CN110280288A (en) * 2019-07-04 2019-09-27 山西师范大学 The preparation method of bifunctional catalyst is precipitated in a kind of nitrogen co-doped carbon material hydrogen reduction of novel transition metal -/oxygen
CN111769297A (en) * 2020-07-17 2020-10-13 郑州佛光发电设备有限公司 Cathode catalyst of aluminum-air battery and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JINPENG WANG等: "ZIF-8 with Ferrocene Encapsulated: A Promising Precursorto Single-Atom Fe Embedded Nitrogen-Doped Carbon asHighly Efficient Catalyst for Oxygen Electroreduction", 《SMALL》 *
YADONG LI等: "Isolated Single Iron Atoms Anchored on N-Doped Porous Carbon asan Efficient Electrocatalyst for the Oxygen Reduction Reaction", 《ANGEW. CHEM.》 *
曹达鹏等: "Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction", 《PNAS》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113477270A (en) * 2021-07-08 2021-10-08 合肥工业大学 Preparation method of copper-iron bimetal confined nitrogen doped carbon nanotube composite material
CN113477270B (en) * 2021-07-08 2023-11-03 合肥工业大学 Preparation method of copper-iron bimetal confined nitrogen-doped carbon nano tube composite material
CN114709436A (en) * 2022-03-02 2022-07-05 北京化工大学 Has Fe2Preparation and application of oxygen evolution/hydrogen evolution/oxygen reduction electrocatalyst with P/Co nano-particle synergistic effect
CN114709436B (en) * 2022-03-02 2024-04-23 北京化工大学 Has Fe2Preparation and application of oxygen evolution/hydrogen evolution/oxygen reduction electrocatalyst with P/Co nano particle synergistic effect
CN114635152A (en) * 2022-03-10 2022-06-17 浙江大学衢州研究院 Preparation method and application of monoatomic dispersion carbon-based catalyst
CN114635152B (en) * 2022-03-10 2023-09-01 浙江大学衢州研究院 Preparation method and application of monoatomic dispersed carbon-based catalyst
CN114976069A (en) * 2022-06-23 2022-08-30 香港科技大学深圳研究院 Preparation method and application of zeolite-like imidazole ester framework/graphene catalyst
CN114976069B (en) * 2022-06-23 2023-11-17 香港科技大学深圳研究院 Preparation method and application of zeolite-like imidazole ester skeleton/graphene catalyst

Similar Documents

Publication Publication Date Title
Fang et al. Unstable Ni leaching in MOF-derived PtNi-C catalyst with improved performance for alcohols fuel electro-oxidation
CN113270595B (en) Nitrogen-doped carbon-supported non-noble metal nano catalyst prepared based on MOF
CN112421062A (en) Preparation method of monoatomic iron dispersion/silver nanoparticle composite structure catalyst
CN107346826A (en) A kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron
CN112652780B (en) Fe/Fe 3 Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst
CN113549935B (en) Heteroatom-doped transition metal monoatomic catalyst and preparation method and application thereof
Tamašauskaitė-Tamašiūnaitė et al. Graphene supported platinum–cobalt nanocomposites as electrocatalysts for borohydride oxidation
CN113270597B (en) C 3 N 4 Coated carbon nano tube loaded NiFe dual-functional oxygen electrocatalyst and preparation method thereof
CN102078816A (en) Selenium/carbon compound material, preparation of selenium/carbon compound material and application of selenium/carbon compound material in fuel-cell catalyst preparation
Huang et al. Chelating agent assisted heat treatment of carbon supported cobalt oxide nanoparticle for use as cathode catalyst of polymer electrolyte membrane fuel cell (PEMFC)
Li et al. MoP-NC nanosphere supported Pt nanoparticles for efficient methanol electrolysis
CN112002915B (en) Oxygen electrode bifunctional catalyst, preparation method and application
CN111957336A (en) Preparation method of ZIF-8-derived Fe-N-C oxygen reduction electrocatalyst
CN114725405B (en) Preparation and application of composite carbon nano-particles loaded with ferrocobalt core-shell structure
Zhang et al. Recent advances in phosphorus containing noble metal electrocatalysts for direct liquid fuel cells
CN110993966A (en) Fuel cell electrocatalyst and preparation method thereof
CN115241470A (en) Carbon nanotube cross-linked iron-nitrogen doped carbon skeleton catalyst and preparation method and application thereof
JP2006134835A (en) Fuel cell and membrane electrode assembly
CN114388819A (en) Preparation method of sub-nanoscale platinum catalyst with high CO tolerance and application of catalyst in fuel cell
CN113410472A (en) Alcohol fuel cell anode catalyst and preparation method thereof
CN113231093A (en) Preparation method and application of FeSb/NC electrocatalyst
Guo et al. Amphiphilic Blocks Copolymer-Stabilized Electro Catalytic Properties of Platinum Nanoparticles for Methanol Electro Oxidation in Acidic Medium
CN115663208A (en) Pt-CuGaO for direct methanol fuel cell anode 2 /C composite catalyst and preparation method thereof
Liang et al. Yolk–shell FeCu/NC electrocatalyst boosting high-performance zinc-air battery
CN116565234A (en) FeMn oxygen reduction electrocatalyst, preparation method and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20210226

RJ01 Rejection of invention patent application after publication