WO2024031917A1 - Bimetallic single-atom nitrogen-doped porous carbon electrocatalyst and preparation method therefor - Google Patents

Bimetallic single-atom nitrogen-doped porous carbon electrocatalyst and preparation method therefor Download PDF

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WO2024031917A1
WO2024031917A1 PCT/CN2022/141460 CN2022141460W WO2024031917A1 WO 2024031917 A1 WO2024031917 A1 WO 2024031917A1 CN 2022141460 W CN2022141460 W CN 2022141460W WO 2024031917 A1 WO2024031917 A1 WO 2024031917A1
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iron
hpnc
porous carbon
nickel
feni
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Chinese (zh)
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杨瑞枝
晏金
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苏州大学
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention belongs to the technical field of high-performance chemical power sources and related battery catalysts, and specifically relates to a preparation method and application of an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst.
  • single-atom catalysts have been widely studied in the fields of chemistry, energy, and environment due to their highest atom utilization, unsaturated coordination structure, and high selectivity and catalytic activity in various catalytic processes.
  • due to the single metal site of single-atom catalysts it is difficult to drive multiple electron transfer processes simultaneously. Therefore, it is still challenging for single-atom catalysts to achieve multifunctional catalytic performance.
  • the coordination environment or electronic structure of single-atom catalysts can be effectively controlled, thereby achieving the purpose of improving bifunctional catalytic activity.
  • bimetallic single-atom catalysts introduce a second metal into the single-atom catalyst, which can not only serve as a new active site, but also regulate the electronic structure of a single metal site, which is considered to improve the bifunctional catalytic efficiency of the catalyst. an effective strategy.
  • the existing technology reports several construction methods for the synthesis of DAC based on wet chemical methods, including solvothermal method, MOF derivatization method, competitive complexation strategy, dual solvent ion deposition method, etc.
  • solvothermal method including MOF derivatization method, competitive complexation strategy, dual solvent ion deposition method, etc.
  • MOF derivatization method competitive complexation strategy
  • dual solvent ion deposition method etc.
  • the synthesis of bimetallic single-atom catalysts is still challenging. , Therefore, it is of great significance to develop a simple and environmentally friendly method to prepare bimetallic single-atom catalysts.
  • the purpose of the present invention is to provide a preparation method and application of an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst in view of the shortcomings in the current technology.
  • the invention not only has a simple preparation process, but also produces materials with high activity and good stability, is low in cost, is environmentally friendly, and is suitable for larger-scale production.
  • the present invention adopts the following technical solution: a method for preparing an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst, which includes the following steps: mixing silicon dioxide, zinc oxide, iron salt, nickel salt, and di-methylimidazole After ball milling, the ball milling product is washed, dried, and then carbonized to obtain an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst.
  • lysine, dodecane, and ethyl orthosilicate are used as raw materials to prepare silica; preferably, lysine and dodecane are dissolved in water, and then ethyl orthosilicate (TEOS) is added , stir for 15 to 25 hours, then heat and age; then dry, and calcine the dried product to obtain silica.
  • TEOS ethyl orthosilicate
  • the silica is a silica sphere with a diameter of 10 to 30 nm.
  • the iron salt is iron nitrate and the nickel salt is nickel nitrate; the molar ratio of zinc oxide, di-methylimidazole, iron salt and nickel salt is (15 ⁇ 20):(35 ⁇ 40):1: 1.
  • the rotation speed of the ball milling treatment is 800-1200 rpm, and the time is 150-200 minutes; preferably, the ball milling is intermittent ball milling, and the interval time is 1-5 minutes.
  • the carbonization treatment is heating from room temperature to 800-1100°C under an inert atmosphere (nitrogen or argon) at a heating rate of 2-8°C ⁇ min -1 , and then continues for 1-4 hours.
  • an inert atmosphere nitrogen or argon
  • the carbonization product is dispersed in an HF solution for 3 to 8 hours, and then washed to obtain an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst, which has a hierarchical porous carbon structure.
  • the invention provides an application of the above-mentioned iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst in zinc-air batteries.
  • the present invention has the following beneficial effects.
  • the electrocatalyst prepared by the present invention uses a simple mechanical ball milling method, is simple to operate, requires no solvent or requires only a small amount of solvent, and is suitable for mass production; the sources of raw materials for preparing the electrocatalyst are abundant and the price is much lower than that of precious metal-based catalysts.
  • the catalyst prepared by the present invention has a hierarchical porous structure, which is conducive to the infiltration of the electrolyte and exposes more active sites; it has an iron-nickel bimetallic active center, and the synergistic effect of the two sites is conducive to promoting electron transfer and accelerating the reaction. kinetics, ultimately improving the bifunctional catalytic efficiency of ORR and OER.
  • Figure 1 shows the XRD diffraction peaks of the catalyst FeNi-HPNC-2 prepared in Example 1.
  • Figure 2 shows the TEM and HADDF-STEM images of the catalyst FeNi-HPNC-2 prepared in Example 1, the STEM image and the N, Ni and Fe element mapping images.
  • Figure 3 shows SEM (a-b) and TEM of Ni-HPNC (c) and HADDF-STEM (d) images.
  • Figure 4 shows SEM (a-b) and TEM of Fe-HPNC (c) and HADDF-STEM (d) images.
  • Figure 5 shows the ORR polarization curves (a) of the synthetic catalysts and commercial Pt/C in 0.1 M KOH solution, the corresponding Tafel curves (b), n values and HO 2 on various catalysts obtained by RRDE measurements.
  • Figure 6 shows the LSV curves of Fe-HPNC, Ni-HPNC and FeNi-HPNC-2, commercial 20%Pt/C and RuO 2 catalysts in 0.1M KOH.
  • Figure 7 shows Fe-NC, Ni-NC, FeNi-NC and FeNi-HPNC-2 catalysts at 0.1 M ORR polarization curve (a) and OER polarization curve (b) in KOH.
  • Figure 8 shows the ORR (a) polarization curve and OER (b) polarization curve of FeNi-HPNC catalysts with different Fe and Ni content ratios in 0.1 M KOH.
  • Figure 9 is a schematic diagram (a) of ZABs using FeNi-HPNC-2 and Pt/C-RuO 2 as air cathodes.
  • silica, zinc oxide, di-methylimidazole, iron nitrate and nickel nitrate are added into a zirconium oxide grinding tank and ball-milled to obtain mixed solid powder; then washed and dried with ethanol, and then the product is transferred to a porcelain boat , carbonization treatment; then the carbonized powder is dispersed in a hydrofluoric acid solution, and then washed repeatedly with deionized water until the pH is 7, and placed in a vacuum oven to dry to obtain the catalyst material, which is an iron-nickel bimetallic single-atom nitrogen Doped porous carbon electrocatalysts.
  • silica is as follows: first, dissolve lysine and dodecane (C 12 H 26 ) in water at 50 to 70°C, then add ethyl orthosilicate (TEOS) and stir continuously. 15 to 25 hours; then transfer the solution to a 100°C oven for aging for 15 to 25 hours; then dry, and heat the resulting product to 600°C for 3 hours to obtain silica.
  • TEOS ethyl orthosilicate
  • the invention adopts a ball milling method to prepare electrocatalysts, which requires almost no solvent, is simple to operate, has low equipment requirements, and the prepared catalyst has high activity and good stability, realizing the preparation of efficient bifunctional oxygen catalysts.
  • the following examples illustrate the method of preparing electrocatalysts by ball milling combined with pyrolysis provided by the present invention.
  • the raw materials of the present invention are existing products, and the specific preparation operations and testing methods are conventional technologies.
  • Example 1 Dissolve 0.146 g lysine and 10.88g C 12 H 26 in 139 ml deionized water at 60°C, add 11.51 mL TEOS to the solution under continuous stirring, keep stirring for 20 hours, and then add The solution was transferred to an oven at 100°C for aging for 20 hours, and then dried. The product was heated at 600°C in air for 3 hours to obtain silica.
  • the TEM image is shown in Figure 1a.
  • FeNi-HPNC catalyst Preparation of FeNi-HPNC catalyst.
  • FeNi-bimetallic center catalyst was synthesized by mechanochemical method. The specific experimental process is as follows: 1.0 g of the above silica, 0.72 g ZnO, 1.47 g 2-methylimidazole, 0.20 g Fe(NO) 3 ⁇ 9H 2 O, 0.14 g Ni(NO) 2 ⁇ 6H 2 O (Fe /Ni molar ratio is 1:1) and 4 ml of ethanol were added to a 100 mL zirconia ball mill jar, and the ball mill jar was placed in a planetary ball mill (CHISHUN, QM3SP2) and ground at 1000 rpm for 6 ⁇ 30 minutes ( Once every 30 minutes, a total of 6 times, with an interval of 2 minutes), then the ball-milled product was washed with ethanol and dried to obtain FeNi-ZIF@SiO 2 , which was transferred to a porcelain boat and heated at 5
  • the heating rate is from room temperature to 1000°C, kept for 2 hours, and then cooled naturally to obtain calcined powder.
  • the calcined powder is evenly dispersed into a 40% HF solution for 6 hours, and then washed with deionized water several times until the pH is 7, and dried in an oven overnight to obtain the final product FeNi-HPNC, named FeNi-HPNC-2, which is an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst.
  • the SEM image is shown in Figure 1b.
  • Example 2 The difference between this example and Example 1 is that the Fe/Ni molar ratio is 1:0 (only 0.404 g Fe(NO) 3 ⁇ 9H 2 O is added), and the product catalyst is named Fe-HPNC.
  • Example 3 The difference between this example and Example 1 is that the Fe/Ni molar ratio is 1:3 (0.101 g Fe(NO) 3 ⁇ 9H 2 O, 0.218 g of Ni(NO) 2 ⁇ 6H 2 O).
  • the product catalyst is named FeNi-HPNC-1.
  • Example 4 The difference between this example and Example 1 is that the Fe/Ni molar ratio is 3:1 (0.303 g Fe(NO) 3 ⁇ 9H 2 O, 0.0726 g of Ni(NO) 2 ⁇ 6H 2 O).
  • the product catalyst is named FeNi-HPNC-3.
  • Example 5 The difference between this example and Example 1 is that the Fe/Ni molar ratio is 0:1 (only 0.291 g Ni(NO) 2 ⁇ 6H 2 O is added), and the product catalyst is named Ni-HPNC.
  • Comparative Example 1 Based on Example 1, silica was omitted to obtain FeNi-NC.
  • FIG. 1c Morphological structure characterization: X-ray diffraction analysis was performed on FeNi-HPNC-2, as shown in Figure 1c. The figure shows two main diffraction peaks. The characteristic peaks at 26° and 44° correspond to carbon respectively. The (002) and (100) crystal planes of the material indicate that the prepared material is mainly carbon structure.
  • Figure 2 (a) and (b) are the transmission electron microscope (TEM) and high-angle annular dark field-scanning transmission electron microscope (HAADF-STEM) images of the prepared catalyst respectively.
  • TEM transmission electron microscope
  • HAADF-STEM high-angle annular dark field-scanning transmission electron microscope
  • the prepared FeNi-HPNC- 2 shows a hierarchical porous structure, and the pore diameter of 20nm is mainly due to the role of silica; the bright spots in the HAADF-STEM image indicate the single atomic dispersed structure, and the adjacent bright spots circled in the circle indicate the presence of the prepared catalyst FeNi bimetallic coordination structure.
  • Figure 2(e) shows the STEM image of FeNi-HPNC-2 and the element mapping image of N, Ni and Fe, illustrating the uniform distribution of N, Ni and Fe in the FeNi-HPNC-2 catalyst.
  • Figures 3 and 4 are the electron microscopy patterns of Ni-HPNC and Fe-HPNC respectively.
  • the CHI 760E electrochemical workstation with a three-electrode system was used to conduct ORR and OER electrochemical performance tests on the prepared catalyst.
  • the three-electrode system consisted of a graphite rod as a counter electrode, Ag/AgCl as a reference electrode, and
  • the working electrode consists of a glassy carbon electrode loaded with catalyst (catalyst loading is 0.4 mg ⁇ cm -2 ). All electrochemical tests were performed in 0.1M KOH electrolyte.
  • FIG. 5 shows the test results.
  • the LSV results (Fig. 5a) show that the ORR activities of Fe-HPNC and Ni-HPNC are relatively low, with half-wave potentials (E 1/2 ) of 0.848V and 0.785V, respectively.
  • the Tafel slope (Fig. 3b) further proves the kinetic activity of the two-atom site catalyst FeNi-HPNC-2. The slope is 54 mVdec -1 , which is smaller than the single-atom site Fe-HPNC (57 mV dec -1 ) and Ni-HPNC.
  • Ni-HPNC (317 mV dec -1 ) and RuO 2 (105 mV dec -1 ) catalysts FeNi- HPNC-2 showed the smallest Tafel slope value of 83 mV dec -1 , indicating good OER kinetics.
  • the results of the ORR accelerated degradation test are shown in Figure 3h. After 10 k cycles of CV, commercial 20%Pt/C showed a significant decrease in activity, with E 1/2 decreasing by 42 mV, while FeNi at the bimetallic site - HPNC-2 showed only a slight loss of activity (2 mV decrease in E 1/2 ), demonstrating the superior stability of FeNi-HPNC-2 towards ORR.
  • FeNi-HPNC-2 with bimetallic sites showed a small potential drop (36 mV) after 1000 CV cycles, while commercial RuO 2 lost potential under the same conditions. reached 130 mV, proving that FeNi-HPNC-2 has excellent OER stability (Figure 3i).
  • FeNi-HPNC The electrochemical performance results of FeNi-HPNC, Fe-HPNC and Ni-HPNC under alkaline conditions show that FeNi-HPNC with bimetallic sites has better oxygen reduction catalytic activity than single-atom Fe-HPNC and Ni-HPNC.
  • the half-wave potential is 0.868V, and the limiting current density is 5.38 mA ⁇ cm -2 .
  • FeNi-HPNC not only has excellent ORR activity, but also shows good electrocatalytic OER activity.
  • the overpotential of FeNi-HPNC at a current density of 10 mA cm -2 is 0.36V, which is lower than 0.49V of Fe-HPNC and 0.56V of Ni-HPNC. It shows that the FeNi-HPNC catalyst with bimetallic sites has excellent bifunctional oxygen catalytic activity, indicating that the catalyst synthesized in the present invention has high practical application value.
  • FIG. 7 shows the ORR and OER performance of Fe-NC, Ni-NC and FeNi-NC electrocatalysts.
  • FeNi-HPNC-2 After adding template silica, a hierarchical porous structure was obtained, which increased the specific surface area and was conducive to the exposure of catalytically active sites, making the obtained FeNi-HPNC-2 better than the bimetal without adding silica.
  • catalysts in zinc-air batteries Disperse the synthesized catalyst (1mg) and acetylene black (0.25mg) in a mixed solution of 10 ⁇ L Nafion (5 wt.%) and 250 ⁇ L ethanol, and conduct ultrasonic treatment for 1 hour to obtain a slurry .
  • the catalyst slurry was evenly dropped on the carbon paper with a loading of 1 mg ⁇ cm -2 as the cathode of the zinc-air battery, and the polished zinc plate was used as the anode.
  • the rechargeable zinc-air battery consists of an air cathode, a zinc anode, and a 6.0 M KOH electrolyte containing 0.2 M zinc acetate.
  • the assembly method is conventional technology.
  • FIG 9 shows the performance test results of rechargeable zinc-air batteries.
  • a rechargeable zinc-air battery (ZAB) was constructed using FeNi-HPNC-2 catalyst as the air cathode and zinc anode.
  • the configuration of the self-assembled ZAB is shown in Figure 9a.
  • Pt/C- RuO2 was also assembled as a catalyst for the air cathode for comparison.
  • the charge-discharge polarization curve in Figure 9b shows that the FeNi-HPNC- 2 based ZAB shows a lower charging voltage at a current density of 300 mA cm - 2 compared with the ZAB assembled with Pt/C-RuO2 catalyst and higher discharge voltage, and the polarization voltage gap is smaller, indicating that FeNi-HPNC-2 has better battery performance.
  • Figure 9c shows that FeNi-HPNC-2 based ZAB has the highest power density of 240 mW cm ⁇ 2 , which is better than Pt/C-RuO 2 (200 mW cm ⁇ 2 ).
  • the ZAB based on FeNi-HPNC-2 shows a higher open circuit voltage (1.48 V) and can continue to discharge for more than 40 hours at a current density of 10 mA cm -2 , while the ZAB based on Pt/C-RuO 2 An obvious voltage drop was observed after 30 hours of discharge, indicating that FeNi-HPNC-2 based ZAB is more stable.
  • the ZAB based on FeNi-HPNC-2 also exhibits a higher specific capacity (815.8 mAh g -1 ), which is better than that of Pt/C-RuO 2 (713.9 mAh g -1 ).
  • the battery performance at different current densities is shown in Figure 9f.
  • the ZAB based on FeNi-HPNC- 2 shows a higher and more stable discharge voltage platform, especially at large current densities. , which indicates that the FeNi-HP-2 assembled ZAB has excellent rate performance.
  • the cycle durability of ZAB was further evaluated through cyclic charge-discharge measurements of 30 minutes of discharge and 30 minutes of charge.
  • the measurement results of XRD, Raman, BET, SEM, HAADF-STEM, and ORR+OER+Zn-air show that: the iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst (FeNi-HPNC) prepared by the method of the present invention , the synthesis method is simple, the cost is low, and it has high bifunctional oxygen catalytic activity, which plays a certain role in promoting the development of low-cost bimetallic single-atom catalysts.
  • FeNi-HPNC iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst
  • FeNi HPNC diatomic iron-nickel anchored on hierarchical porous nitrogen-doped carbon

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Abstract

Disclosed in the present invention are a preparation method for a FeNi bimetallic single-atom nitrogen-doped porous carbon (FeNi-HPNC) electrocatalyst and a use of the electrocatalyst. The preparation method comprises: mixing and ball-milling silicon dioxide, zinc oxide, a ferric salt, a nickel salt, and 2-Methylimidazole, then washing and drying a ball-milled product, and performing carbonization treatment to obtain a FeNi-HPNC electrocatalyst. In the present invention, a high-energy ball milling and simple mechanochemical method is used, nickel is introduced to be coordinated with monatomic iron, the electronic structure is adjusted, and the synthesized catalyst has an atomically dispersed bimetallic active center and a rich hierarchical porous structure. The interaction of electrons of bimetallic sites can reduce the adsorption energy of an oxygen intermediate, showing significant bifunctional oxygen catalytic activity. FeNi-HPNC has an ORR half-wave potential of as high as 0.868 V, and an OER potential of as low as 1.59 V at 10 mA cm-2, is obviously superior to Fe-HPNC and Ni-HPNC single-atom catalysts, even better than a noble metal catalyst, and can be applied to energy storage and conversion devices such as fuel cells and metal-air batteries.

Description

一种双金属单原子氮掺杂多孔碳电催化剂及其制备方法A bimetallic single-atom nitrogen-doped porous carbon electrocatalyst and its preparation method 技术领域Technical field
本发明属于高性能化学电源及相关电池催化剂技术领域，具体涉及一种铁镍双金属单原子氮掺杂多孔碳电催化剂的制备方法与应用。The invention belongs to the technical field of high-performance chemical power sources and related battery catalysts, and specifically relates to a preparation method and application of an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst.
背景技术Background technique
发展清洁高效和可持续的能量储存和转换体系是解决当今世界日益加剧的能源危机和环境污染的根本出路。在众多能量储存和转换系统中，锌空气电池由于其具有能量密度高，成本低廉，环境友好等优点受到了广泛的关注。但是，锌空气电池在工作时，其空气电极处氧气还原反应(Oxygen Reduction Reaction, ORR）和氧气析出反应（Oxygen Evolution Reaction, OER）动力学过程缓慢，通常需要高效的催化剂降低反应能垒，提高电化学反应速率。目前商用的催化剂主要是贵金属基催化剂，但是其储量稀少，价格昂贵，稳定性差等缺点限制了发展，而且一种贵金属基催化剂催化活性单一，无法同时满足多种催化反应。Developing clean, efficient and sustainable energy storage and conversion systems is the fundamental way to solve the increasing energy crisis and environmental pollution in today's world. Among numerous energy storage and conversion systems, zinc-air batteries have received widespread attention due to their high energy density, low cost, and environmental friendliness. However, when the zinc-air battery is working, the oxygen reduction reaction (Oxygen) at the air electrode Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) kinetic process is slow, and efficient catalysts are usually required to reduce the reaction energy barrier and increase the electrochemical reaction rate. Currently, commercially available catalysts are mainly precious metal-based catalysts, but their short reserves, high price, and poor stability limit their development. Moreover, a precious metal-based catalyst has a single catalytic activity and cannot satisfy multiple catalytic reactions at the same time.
目前，单原子催化剂由于其具有最高的原子利用率，不饱和配位结构，以及各种催化过程中表现出的高选择性和催化活性，已在化学、 能源及环境等领域得到了广泛研究。然而，由于单原子催化剂的单一金属位点，很难同时驱动多电子转移过程，因此，单原子催化剂要实现多功能催化性能仍然具有挑战性。近年来，通过引入第二金属原子，杂原子，或者缺陷等，可以有效的调控单原子催化剂的配位环境或电子结构，从而达到提高双功能催化活性的目的。其中, 双金属单原子催化剂(DAC)在单原子催化剂种引入第二种金属，不仅可以作为新的活性位点，还可以调控单一金属位点的电子结构，被认为是提高催化剂双功能催化效率的一种有效的策略。现有技术报道了几种基于湿化学法合成DAC的构建方法，包括溶剂热法、MOF衍生法、竞争络合策略、双溶剂离子沉积法等，目前对于双金属单原子催化剂的合成仍具有挑战，因此，研发一种工艺简单，环境友好方法制备双金属单原子催化剂具有重要意义。Currently, single-atom catalysts have been widely studied in the fields of chemistry, energy, and environment due to their highest atom utilization, unsaturated coordination structure, and high selectivity and catalytic activity in various catalytic processes. However, due to the single metal site of single-atom catalysts, it is difficult to drive multiple electron transfer processes simultaneously. Therefore, it is still challenging for single-atom catalysts to achieve multifunctional catalytic performance. In recent years, by introducing second metal atoms, heteroatoms, or defects, the coordination environment or electronic structure of single-atom catalysts can be effectively controlled, thereby achieving the purpose of improving bifunctional catalytic activity. Among them, bimetallic single-atom catalysts (DAC) introduce a second metal into the single-atom catalyst, which can not only serve as a new active site, but also regulate the electronic structure of a single metal site, which is considered to improve the bifunctional catalytic efficiency of the catalyst. an effective strategy. The existing technology reports several construction methods for the synthesis of DAC based on wet chemical methods, including solvothermal method, MOF derivatization method, competitive complexation strategy, dual solvent ion deposition method, etc. Currently, the synthesis of bimetallic single-atom catalysts is still challenging. , Therefore, it is of great significance to develop a simple and environmentally friendly method to prepare bimetallic single-atom catalysts.
技术问题technical problem
本发明的目的是针对当前技术中存在的不足，提供一种铁镍双金属单原子氮掺杂多孔碳电催化剂的制备方法与应用。本发明不仅制备过程简便，制备出的材料活性高，稳定性好，而且成本低，环境友好，适用于较大规模生产。The purpose of the present invention is to provide a preparation method and application of an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst in view of the shortcomings in the current technology. The invention not only has a simple preparation process, but also produces materials with high activity and good stability, is low in cost, is environmentally friendly, and is suitable for larger-scale production.
技术解决方案Technical solutions
本发明采用如下技术方案：一种铁镍双金属单原子氮掺杂多孔碳电催化剂的制备方法，包括如下步骤：将二氧化硅、氧化锌、铁盐、镍盐、二-甲基咪唑混合球磨，然后将球磨产物洗涤干燥，再碳化处理，得到铁镍双金属单原子氮掺杂多孔碳电催化剂。The present invention adopts the following technical solution: a method for preparing an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst, which includes the following steps: mixing silicon dioxide, zinc oxide, iron salt, nickel salt, and di-methylimidazole After ball milling, the ball milling product is washed, dried, and then carbonized to obtain an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst.
本发明中，以赖氨酸、十二烷、正硅酸乙酯为原料制备二氧化硅；优选的，将赖氨酸和十二烷溶解于水中，随后加入正硅酸乙酯 （TEOS），搅拌15～25 小时，然后加热老化；然后干燥，将干燥产物煅烧，得到二氧化硅。优选的，所述二氧化硅为二氧化硅球，直径为10～30 nm。In the present invention, lysine, dodecane, and ethyl orthosilicate are used as raw materials to prepare silica; preferably, lysine and dodecane are dissolved in water, and then ethyl orthosilicate (TEOS) is added , stir for 15 to 25 hours, then heat and age; then dry, and calcine the dried product to obtain silica. Preferably, the silica is a silica sphere with a diameter of 10 to 30 nm.
本发明中，所述铁盐为硝酸铁、镍盐为硝酸镍；氧化锌、二-甲基咪唑、铁盐、镍盐的摩尔比为 （15～20）∶（35～40）∶1∶1。In the present invention, the iron salt is iron nitrate and the nickel salt is nickel nitrate; the molar ratio of zinc oxide, di-methylimidazole, iron salt and nickel salt is (15~20):(35~40):1: 1.
本发明中，所述球磨处理的转速为800～1200 rpm，时间为150～200分钟；优选的，球磨为间歇球磨，间隔时间为1～5分钟。In the present invention, the rotation speed of the ball milling treatment is 800-1200 rpm, and the time is 150-200 minutes; preferably, the ball milling is intermittent ball milling, and the interval time is 1-5 minutes.
本发明中，所述碳化处理是惰性气氛（氮气或者氩气）条件下以2～8℃·min -1的升温速率由室温加热到800～1100℃，然后持续1～4小时。 In the present invention, the carbonization treatment is heating from room temperature to 800-1100°C under an inert atmosphere (nitrogen or argon) at a heating rate of 2-8°C·min -1 , and then continues for 1-4 hours.
本发明中，碳化处理后，将碳化产物分散在HF溶液中3～8小时，然后洗涤，得到铁镍双金属单原子氮掺杂多孔碳电催化剂，所述电催化剂具有分级多孔碳结构。In the present invention, after carbonization treatment, the carbonization product is dispersed in an HF solution for 3 to 8 hours, and then washed to obtain an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst, which has a hierarchical porous carbon structure.
本发明提供了一种上述铁镍双金属单原子氮掺杂多孔碳电催化剂在锌-空气电池中的应用。The invention provides an application of the above-mentioned iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst in zinc-air batteries.
有益效果beneficial effects
与现有技术相比，本发明具有以下有益效果。Compared with the prior art, the present invention has the following beneficial effects.
（1）本发明制备的电催化剂使用简单的机械球磨法，操作简单，无需溶剂或者只需少量溶剂，适用于大批量生产；制备电催化剂的原料来源丰富，价格远低于贵金属基催化剂。(1) The electrocatalyst prepared by the present invention uses a simple mechanical ball milling method, is simple to operate, requires no solvent or requires only a small amount of solvent, and is suitable for mass production; the sources of raw materials for preparing the electrocatalyst are abundant and the price is much lower than that of precious metal-based catalysts.
（2）本发明制备的催化剂具有分级多孔结构，有利于电解液的浸润，暴露更多的活性位点；具有铁镍双金属活性中心，双位点的协同效应有利于促进电子转移，加速反应动力学，最终提高ORR和OER双功能催化效率。(2) The catalyst prepared by the present invention has a hierarchical porous structure, which is conducive to the infiltration of the electrolyte and exposes more active sites; it has an iron-nickel bimetallic active center, and the synergistic effect of the two sites is conducive to promoting electron transfer and accelerating the reaction. kinetics, ultimately improving the bifunctional catalytic efficiency of ORR and OER.
附图说明Description of drawings
图1为实施例一制备的催化剂FeNi-HPNC-2的XRD衍射峰。Figure 1 shows the XRD diffraction peaks of the catalyst FeNi-HPNC-2 prepared in Example 1.
图2为实施例一制备的催化剂FeNi-HPNC-2的TEM和HADDF-STEM图，STEM图像和N、Ni和Fe元素映射图像。Figure 2 shows the TEM and HADDF-STEM images of the catalyst FeNi-HPNC-2 prepared in Example 1, the STEM image and the N, Ni and Fe element mapping images.
图3为Ni-HPNC的SEM (a-b) 、TEM (c) 和HADDF-STEM(d)图。Figure 3 shows SEM (a-b) and TEM of Ni-HPNC (c) and HADDF-STEM (d) images.
图4为Fe-HPNC的SEM (a-b) 、TEM (c) 和HADDF-STEM(d)图。Figure 4 shows SEM (a-b) and TEM of Fe-HPNC (c) and HADDF-STEM (d) images.
图5为合成催化剂和商用Pt/C在0.1M KOH溶液中的ORR极化曲线(a)，相应的塔菲尔曲线(b)，通过RRDE测量获得的各种催化剂上的n值和HO 2-百分比(c)，合成催化剂和商业RuO 2在0.1M KOH溶液中的OER极化曲线(d)，相应的塔菲尔曲线(e) EIS结果和相应的等效电路(f)，所有合成催化剂Pt/C和RuO 2的E 1/2和E j =10之间的电位差比较(g)， 10000次循环前后FeNi-HPNC-2和Pt/C的ORR极化曲线(h)， 1000次循环前后FeNi-HPNC-2和RuO 2的OER极化曲线(i)。 Figure 5 shows the ORR polarization curves (a) of the synthetic catalysts and commercial Pt/C in 0.1 M KOH solution, the corresponding Tafel curves (b), n values and HO 2 on various catalysts obtained by RRDE measurements. - Percentage (c), OER polarization curves (d) of synthesized catalysts and commercial RuO2 in 0.1 M KOH solution, corresponding Tafel curve (e) EIS results and corresponding equivalent circuit (f), all syntheses Comparison of the potential difference between E 1/2 and E j =10 of the catalysts Pt/C and RuO 2 (g), ORR polarization curves of FeNi-HPNC-2 and Pt/C before and after 10000 cycles (h), 1000 OER polarization curves (i) of FeNi-HPNC- 2 and RuO before and after the second cycle.
图6为Fe-HPNC、Ni-HPNC和FeNi-HPNC-2、商用20%Pt/C和RuO 2催化剂在0.1M KOH中的LSV曲线。 Figure 6 shows the LSV curves of Fe-HPNC, Ni-HPNC and FeNi-HPNC-2, commercial 20%Pt/C and RuO 2 catalysts in 0.1M KOH.
图7为Fe-NC、Ni-NC、FeNi-NC 和FeNi-HPNC-2催化剂在0.1 M KOH中的ORR极化曲线 (a)和OER极化曲线 (b)。Figure 7 shows Fe-NC, Ni-NC, FeNi-NC and FeNi-HPNC-2 catalysts at 0.1 M ORR polarization curve (a) and OER polarization curve (b) in KOH.
图8为不同Fe, Ni含量比的FeNi-HPNC催化剂在0.1 M KOH中的ORR (a)极化曲线、OER (b)极化曲线。Figure 8 shows the ORR (a) polarization curve and OER (b) polarization curve of FeNi-HPNC catalysts with different Fe and Ni content ratios in 0.1 M KOH.
图9为FeNi-HPNC-2和Pt/C-RuO 2作为空气阴极的ZABs示意图(a)。充放电极化曲线(b)和功率密度曲线图(c)。电流密度为10mA cm -2时的恒电流放电曲线(d)和对应的比容量曲线(e)。不同电流密度下的恒电流放电曲线(f)。以及在10 mA cm -2下的长期循环性能(g)。由两个串联的ZAB供电点亮LED灯泡的光学照片(h)。 Figure 9 is a schematic diagram (a) of ZABs using FeNi-HPNC-2 and Pt/C-RuO 2 as air cathodes. Charge-discharge polarization curve (b) and power density curve (c). The galvanostatic discharge curve (d) and the corresponding specific capacity curve (e) when the current density is 10mA cm -2 . Galvanostatic discharge curves (f) under different current densities. and long-term cycling performance (g) at 10 mA cm -2 . Optical photo of an LED bulb powered by two series-connected ZABs (h).
本发明的实施方式Embodiments of the invention
本发明将二氧化硅、氧化锌、二-甲基咪唑、硝酸铁和硝酸镍加入氧化锆研磨罐中，球磨，得到混合固体粉末；然后用乙醇洗涤并干燥，再将产物转移到瓷舟中，碳化处理；然后将碳化得到的粉末分散在氢氟酸溶液中，然后用去离子水反复洗涤，直到pH为7，放入真空烘箱中干燥，得到催化剂材料，为铁镍双金属单原子氮掺杂多孔碳电催化剂。In the present invention, silica, zinc oxide, di-methylimidazole, iron nitrate and nickel nitrate are added into a zirconium oxide grinding tank and ball-milled to obtain mixed solid powder; then washed and dried with ethanol, and then the product is transferred to a porcelain boat , carbonization treatment; then the carbonized powder is dispersed in a hydrofluoric acid solution, and then washed repeatedly with deionized water until the pH is 7, and placed in a vacuum oven to dry to obtain the catalyst material, which is an iron-nickel bimetallic single-atom nitrogen Doped porous carbon electrocatalysts.
进一步地，二氧化硅的制备如下：首先，在50～70℃下，将赖氨酸和十二烷（C 12H 26）溶解于水中，随后加入正硅酸乙酯 （TEOS），连续搅拌15～25小时；再将溶液转移到100℃烘箱中老化15～25小时；然后干燥，将所得产物加热到600℃持续3小时，得到二氧化硅。 Further, the preparation of silica is as follows: first, dissolve lysine and dodecane (C 12 H 26 ) in water at 50 to 70°C, then add ethyl orthosilicate (TEOS) and stir continuously. 15 to 25 hours; then transfer the solution to a 100°C oven for aging for 15 to 25 hours; then dry, and heat the resulting product to 600°C for 3 hours to obtain silica.
本发明采用球磨法制备电催化剂，几乎不用溶剂、操作简单、对设备要求低，所制备的催化剂活性高、稳定性好，实现高效的双功能氧催化剂的制备。以下示例说明了本发明提供的球磨法结合热解制备电催化剂的方法。本发明的原料为现有产品，具体制备操作以及测试方法为常规技术。The invention adopts a ball milling method to prepare electrocatalysts, which requires almost no solvent, is simple to operate, has low equipment requirements, and the prepared catalyst has high activity and good stability, realizing the preparation of efficient bifunctional oxygen catalysts. The following examples illustrate the method of preparing electrocatalysts by ball milling combined with pyrolysis provided by the present invention. The raw materials of the present invention are existing products, and the specific preparation operations and testing methods are conventional technologies.
实施例一：在60℃下，将0.146 g赖氨酸和10.88g C 12H 26溶解在139 ml去离子水中，在连续搅拌下将11.51mL TEOS 加入到溶液中，保持搅拌20 小时，然后将溶液转移到100℃烘箱中老化20 小时，再干燥，将产物在空气中600℃加热3小时，得到二氧化硅，TEM图见图1a。 Example 1: Dissolve 0.146 g lysine and 10.88g C 12 H 26 in 139 ml deionized water at 60°C, add 11.51 mL TEOS to the solution under continuous stirring, keep stirring for 20 hours, and then add The solution was transferred to an oven at 100°C for aging for 20 hours, and then dried. The product was heated at 600°C in air for 3 hours to obtain silica. The TEM image is shown in Figure 1a.
FeNi-HPNC催化剂的制备。采用机械化学法合成了FeNi-双金属中心催化剂。具体实验过程如下:将1.0 g上述二氧化硅、0.72 g ZnO、1.47 g 2-甲基咪唑、0.20 g Fe(NO) 3·9H 2O、0.14 g Ni(NO) 2·6H 2O (Fe/Ni的摩尔比为1∶1)以及4 ml乙醇加入到100 mL 氧化锆球磨罐中，将球磨罐置于行星式球磨机(CHISHUN，QM3SP2)中，以1000 rpm的转速研磨6×30分钟（30分钟一次，共6次，间歇2分钟），然后将球磨产物用乙醇洗涤并干燥，得到FeNi-ZIF@SiO 2，将其转移到瓷舟中，在氮气下以5 °C·min -1的升温速率由室温加热至1000℃，保温2 小时，然后自然冷却，得到煅烧粉末，将煅烧后的粉末均匀分散到40%的HF溶液中6小时，再用去离子水洗涤多次，直到pH为7，在烘箱中干燥过夜，得到最终产物FeNi-HPNC，命名为FeNi-HPNC-2，为铁镍双金属单原子氮掺杂多孔碳电催化剂，SEM图见图1b。 Preparation of FeNi-HPNC catalyst. FeNi-bimetallic center catalyst was synthesized by mechanochemical method. The specific experimental process is as follows: 1.0 g of the above silica, 0.72 g ZnO, 1.47 g 2-methylimidazole, 0.20 g Fe(NO) 3 ·9H 2 O, 0.14 g Ni(NO) 2 ·6H 2 O (Fe /Ni molar ratio is 1:1) and 4 ml of ethanol were added to a 100 mL zirconia ball mill jar, and the ball mill jar was placed in a planetary ball mill (CHISHUN, QM3SP2) and ground at 1000 rpm for 6 × 30 minutes ( Once every 30 minutes, a total of 6 times, with an interval of 2 minutes), then the ball-milled product was washed with ethanol and dried to obtain FeNi-ZIF@SiO 2 , which was transferred to a porcelain boat and heated at 5 °C·min -1 under nitrogen. The heating rate is from room temperature to 1000°C, kept for 2 hours, and then cooled naturally to obtain calcined powder. The calcined powder is evenly dispersed into a 40% HF solution for 6 hours, and then washed with deionized water several times until the pH is 7, and dried in an oven overnight to obtain the final product FeNi-HPNC, named FeNi-HPNC-2, which is an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst. The SEM image is shown in Figure 1b.
实施例二：本实施例与实施例一的区别在于Fe/Ni摩尔比为1:0（只加入0.404 g Fe(NO) 3·9H 2O），产物催化剂命名为Fe-HPNC。 Example 2: The difference between this example and Example 1 is that the Fe/Ni molar ratio is 1:0 (only 0.404 g Fe(NO) 3 ·9H 2 O is added), and the product catalyst is named Fe-HPNC.
实施例三：本实施例与实施例一的区别在于Fe/Ni摩尔比为1:3（0.101 g Fe(NO) 3·9H 2O、0.218 g of Ni(NO) 2·6H 2O），产物催化剂命名为FeNi-HPNC-1。 Example 3: The difference between this example and Example 1 is that the Fe/Ni molar ratio is 1:3 (0.101 g Fe(NO) 3 ·9H 2 O, 0.218 g of Ni(NO) 2 ·6H 2 O). The product catalyst is named FeNi-HPNC-1.
实施例四：本实施例与实施例一的区别在于Fe/Ni摩尔比为3:1（0.303 g Fe(NO) 3·9H 2O、0.0726 g of Ni(NO) 2·6H 2O），产物催化剂命名为FeNi-HPNC-3。 Example 4: The difference between this example and Example 1 is that the Fe/Ni molar ratio is 3:1 (0.303 g Fe(NO) 3 ·9H 2 O, 0.0726 g of Ni(NO) 2 ·6H 2 O). The product catalyst is named FeNi-HPNC-3.
实施例五：本实施例与实施例一的区别在于Fe/Ni摩尔比为0:1（只加入0.291 g Ni(NO) 2·6H 2O），产物催化剂命名为Ni-HPNC。 Example 5: The difference between this example and Example 1 is that the Fe/Ni molar ratio is 0:1 (only 0.291 g Ni(NO) 2 ·6H 2 O is added), and the product catalyst is named Ni-HPNC.
对比例一：在实施例一的基础上，省略二氧化硅，得到FeNi-NC。Comparative Example 1: Based on Example 1, silica was omitted to obtain FeNi-NC.
在实施例二的基础上，省略二氧化硅，得到Fe-NC。On the basis of Example 2, silica is omitted to obtain Fe-NC.
在实施例五的基础上，省略二氧化硅，得到Ni-NC。On the basis of Example 5, silica is omitted to obtain Ni-NC.
形貌结构表征：对FeNi-HPNC-2进行了X-射线衍射分析，如图1c所示，图中显示了两个主要的衍射峰，在26° 和44°处的特征峰分别对应于碳材料的(002)和(100)晶面， 表明所制备的材料主要为碳结构。图2 (a)和(b)分别为所制备催化剂的透射电子显微镜图(TEM)和高角环形暗场-扫描透射电子显微镜(HAADF-STEM)图像，可以看出，所制备的FeNi-HPNC-2呈现出分级多孔的结构，且在20nm 的孔径主要是二氧化硅的作用；HAADF-STEM 图中的亮点表明了单个的原子分散结构，且圆圈圈出的相邻亮点表明所制备的催化剂存在FeNi 双金属配位结构。图2(e)为FeNi-HPNC-2的STEM图像和N、Ni和Fe元素映射图像，说明了N、Ni和Fe在FeNi-HPNC-2催化剂中的均匀分布。图3 和图4分别为Ni-HPNC和Fe-HPNC的电子显微镜图谱，SEM(图3a-b, 图4a-b)和TEM(图3c, 图4c)结果表明所制备的Ni-HPNC和Fe-HPNC催化剂呈现出分级多孔的结构，且图中未观察到明显的金属合金或颗粒区域，结合HAADF-STEM(图3d, 图4d)中相应的单个原子亮点，进一步证明所制备的Ni-HPNC和Fe-HPNC为单原子活性位结构。Morphological structure characterization: X-ray diffraction analysis was performed on FeNi-HPNC-2, as shown in Figure 1c. The figure shows two main diffraction peaks. The characteristic peaks at 26° and 44° correspond to carbon respectively. The (002) and (100) crystal planes of the material indicate that the prepared material is mainly carbon structure. Figure 2 (a) and (b) are the transmission electron microscope (TEM) and high-angle annular dark field-scanning transmission electron microscope (HAADF-STEM) images of the prepared catalyst respectively. It can be seen that the prepared FeNi-HPNC- 2 shows a hierarchical porous structure, and the pore diameter of 20nm is mainly due to the role of silica; the bright spots in the HAADF-STEM image indicate the single atomic dispersed structure, and the adjacent bright spots circled in the circle indicate the presence of the prepared catalyst FeNi bimetallic coordination structure. Figure 2(e) shows the STEM image of FeNi-HPNC-2 and the element mapping image of N, Ni and Fe, illustrating the uniform distribution of N, Ni and Fe in the FeNi-HPNC-2 catalyst. Figures 3 and 4 are the electron microscopy patterns of Ni-HPNC and Fe-HPNC respectively. The SEM (Figure 3a-b, Figure 4a-b) and TEM (Figure 3c, Figure 4c) results show that the prepared Ni-HPNC and Fe -HPNC catalyst exhibits a hierarchical porous structure, and no obvious metal alloy or particle area is observed in the figure. Combined with the corresponding single atomic bright spots in HAADF-STEM (Figure 3d, Figure 4d), it further proves that the prepared Ni-HPNC And Fe-HPNC is a single-atom active site structure.
性能测试：采用具有三电极系统的CHI 760E电化学工作站对所制备的催化剂进行ORR和OER电化学性能测试，该三电极系统由作为对电极的石墨棒、作为参比电极的Ag/AgCl和作为工作电极的负载有催化剂(催化剂负载为0.4mg·cm -2)的玻璃碳电极组成。所有的电化学测试都是在0.1M KOH电解液中进行的。对于ORR，首先在N 2饱和溶液和O 2饱和溶液中以50 mV s -1的扫描速率进行循环伏安法测试，其次以5 mV s -1的扫描速率在1600 rpm的转速下进行线性扫描伏安(LSV)测试。对于OER，在N 2饱和电解液中，以5 mV·s -1的扫描速率，电位区间为0.96~1.96 V下进行LSV测试。催化剂浆料制备：将催化剂(5mg)分散在Nafion与350 mL乙醇的混合溶液中，超声30分钟以上以形成均匀的浆料，然后涂在玻璃碳电极上，形成工作电极。以上除了催化剂为本发明实施例或者对比例产物外，其余为现有技术。本发明实施例中极化曲线的所有电位都转换为可逆氢电极(RHE, E RHE = E Ag/AgCl + E 0Ag/AgCl +0.059pH)。 Performance test: The CHI 760E electrochemical workstation with a three-electrode system was used to conduct ORR and OER electrochemical performance tests on the prepared catalyst. The three-electrode system consisted of a graphite rod as a counter electrode, Ag/AgCl as a reference electrode, and The working electrode consists of a glassy carbon electrode loaded with catalyst (catalyst loading is 0.4 mg·cm -2 ). All electrochemical tests were performed in 0.1M KOH electrolyte. For ORR, cyclic voltammetry tests were performed first at a scan rate of 50 mV s -1 in N2 - saturated solutions and O2 - saturated solutions, and secondly at a scan rate of 5 mV s -1 at a rotational speed of 1600 rpm. Voltammetry (LSV) test. For OER, LSV testing was performed in N saturated electrolyte at a scan rate of 5 mV·s -1 and a potential range of 0.96~1.96 V. Catalyst slurry preparation: Disperse the catalyst (5 mg) in a mixed solution of Nafion and 350 mL ethanol, ultrasonic for more than 30 minutes to form a uniform slurry, and then coat it on the glassy carbon electrode to form a working electrode. Except for the catalysts described above which are the products of the examples or comparative examples of the present invention, the rest are existing technologies. All potentials of the polarization curve in the embodiment of the present invention are converted to reversible hydrogen electrodes (RHE, E RHE = E Ag/AgCl + E 0Ag/AgCl + 0.059pH).
图5为测试结果。LSV结果(图5a)表明，Fe-HPNC和Ni-HPNC的ORR活性相对较低，半波电位(E 1/2)分别为0.848V和0.785V。而双金属位点的FeNi-HPNC-2催化剂表现出较高的ORR活性，E 1/2值为0.868V，甚至高于商用Pt/C(碳上含20%Pt，E 1/2=0.858V)。Tafel斜率(图3b)进一步证明了双原子位催化剂FeNi-HPNC-2的动力学活性，该斜率为54 mVdec -1，小于单原子位的Fe-HPNC(57 mV dec -1)以及Ni-HPNC (74 mV dec -1)催化剂；所制备催化剂的过氧化物种类的产率和电子转移数如图3c所示，FeNi-HPNC-2的HO 2 -产率低于5%，且电子转移数接近4.0，表明其具有优异的四电子选择性。催化剂的OER活性如图3d所示，双金属位点的FeNi-HPNC-2在10mA cm -2的电流密度下表现出0.36V的过电位(E j =10),远低于单原子位点的Fe-HPNC (E j =10=0.49V) 和Ni-HPNC (E j =10=0.56V)催化剂，甚至低于商用RuO 2催化剂(E j =10=0.39V)，证明双金属位点的FeNi-HPNC-2具有较好的OER活性。在OER相应的Tafel斜率(图3e)中，与Fe-HPNC(123 mV dec -1)、Ni-HPNC(317 mV dec -1)和RuO 2(105 mV dec -1)催化剂相比， FeNi-HPNC-2显示出最小的Tafel斜率数值83 mV dec -1，表明其具有良好的OER动力学。用电化学阻抗谱（EIS）进一步研究了OER动力学。如图3f所示，双金属位点的FeNi-HPNC-2的半圆直径明显小于对照催化剂，表明在OER过程中整体阻抗较低，反应动力学较快。除此之外，我们还通过OER的E j ＝ 10与ORR的E 1/2之间的电位差值评估了催化剂的双功能催化活性(∆E)。如图3g和图6所示，双金属位点的FeNi-HPNC-2的∆E值(0.72V)明显小于单原子位点的Fe-HPNC (∆E=0.88V)，Ni-HPNC(∆E=1.00V)以及商用Pt/C(∆E＝0.90V)、RuO 2(∆E=1.02V)，表明其优异的双功能催化活性。此外，还测量了FeNi-HPNC-2的耐久性，并将其与商用Pt/C和RuO 2的耐久性进行了比较。ORR加速降解试验的结果如图3h所示，在循环了10 k 圈CV后，商用20%Pt/C表现出显著的活性下降，E 1/2下降了42 mV，而双金属位点的FeNi-HPNC-2中仅显示出轻微的活性损失(E 1/2 下降2 mV)，证明了FeNi-HPNC-2对ORR的优越稳定性。对OER的稳定性也进行了同样的测试，双金属位点的FeNi-HPNC-2在1000 圈CV循环后的表现出小的电位降(36 mV), 而商业RuO 2在相同条件下电位损失了130 mV，证明FeNi-HPNC-2具有优异的OER稳定性(图3i)。 Figure 5 shows the test results. The LSV results (Fig. 5a) show that the ORR activities of Fe-HPNC and Ni-HPNC are relatively low, with half-wave potentials (E 1/2 ) of 0.848V and 0.785V, respectively. The FeNi-HPNC-2 catalyst with bimetallic sites shows high ORR activity, with an E 1/2 value of 0.868V, even higher than commercial Pt/C (containing 20% Pt on carbon, E 1/2 =0.858 V). The Tafel slope (Fig. 3b) further proves the kinetic activity of the two-atom site catalyst FeNi-HPNC-2. The slope is 54 mVdec -1 , which is smaller than the single-atom site Fe-HPNC (57 mV dec -1 ) and Ni-HPNC. (74 mV dec -1 ) catalyst; the yield and electron transfer number of peroxide species of the prepared catalyst are shown in Figure 3c. The HO 2 - yield of FeNi-HPNC-2 is less than 5%, and the electron transfer number Close to 4.0, indicating excellent four-electron selectivity. The OER activity of the catalyst is shown in Figure 3d. FeNi-HPNC-2 at the bimetallic site exhibits an overpotential of 0.36V (E j =10 ) at a current density of 10mA cm -2 , which is much lower than that of the single-atom site. The Fe-HPNC (E j =10 =0.49V) and Ni-HPNC (E j =10 =0.56V) catalysts are even lower than the commercial RuO 2 catalyst (E j =10 =0.39V), proving the bimetallic sites FeNi-HPNC-2 has better OER activity. In the corresponding Tafel slope of OER (Fig. 3e), compared with Fe-HPNC (123 mV dec -1 ), Ni-HPNC (317 mV dec -1 ) and RuO 2 (105 mV dec -1 ) catalysts, FeNi- HPNC-2 showed the smallest Tafel slope value of 83 mV dec -1 , indicating good OER kinetics. The OER kinetics were further studied using electrochemical impedance spectroscopy (EIS). As shown in Figure 3f, the semicircle diameter of FeNi-HPNC-2 at bimetallic sites is significantly smaller than that of the control catalyst, indicating that the overall impedance is lower and the reaction kinetics is faster during the OER process. In addition, we also evaluated the bifunctional catalytic activity (ΔE) of the catalyst through the potential difference between E j = 10 for OER and E 1/2 for ORR. As shown in Figure 3g and Figure 6, the ΔE value (0.72V) of FeNi-HPNC-2 at the bimetallic site is significantly smaller than that of Fe-HPNC (ΔE=0.88V) at the single-atom site. Ni-HPNC (Δ E=1.00V) as well as commercial Pt/C (ΔE=0.90V) and RuO 2 (ΔE=1.02V), indicating its excellent bifunctional catalytic activity. Furthermore, the durability of FeNi-HPNC-2 was measured and compared with that of commercial Pt/C and RuO2 . The results of the ORR accelerated degradation test are shown in Figure 3h. After 10 k cycles of CV, commercial 20%Pt/C showed a significant decrease in activity, with E 1/2 decreasing by 42 mV, while FeNi at the bimetallic site - HPNC-2 showed only a slight loss of activity (2 mV decrease in E 1/2 ), demonstrating the superior stability of FeNi-HPNC-2 towards ORR. The same test was conducted on the stability of OER. FeNi-HPNC-2 with bimetallic sites showed a small potential drop (36 mV) after 1000 CV cycles, while commercial RuO 2 lost potential under the same conditions. reached 130 mV, proving that FeNi-HPNC-2 has excellent OER stability (Figure 3i).
碱性条件下的FeNi-HPNC， Fe-HPNC以及Ni-HPNC的电化学性能结果表明中，双金属位点的FeNi-HPNC具有优于单原子Fe-HPNC, Ni-HPNC氧还原催化活性，其半波电位为0.868V，极限电流密度为5.38 mA·cm -2。FeNi-HPNC不仅具有的优异的ORR活性，它还显示出良好的电催化OER活性。 FeNi-HPNC在10 mA cm -2的电流密度下的过电势为0.36V，低于Fe-HPNC 的0.49V 、Ni-HPNC 0.56V。说明双金属位点的FeNi-HPNC催化剂具有优异的双功能氧催化活性，说明本发明合成的催化剂具有高的实际应用价值。 The electrochemical performance results of FeNi-HPNC, Fe-HPNC and Ni-HPNC under alkaline conditions show that FeNi-HPNC with bimetallic sites has better oxygen reduction catalytic activity than single-atom Fe-HPNC and Ni-HPNC. The half-wave potential is 0.868V, and the limiting current density is 5.38 mA·cm -2 . FeNi-HPNC not only has excellent ORR activity, but also shows good electrocatalytic OER activity. The overpotential of FeNi-HPNC at a current density of 10 mA cm -2 is 0.36V, which is lower than 0.49V of Fe-HPNC and 0.56V of Ni-HPNC. It shows that the FeNi-HPNC catalyst with bimetallic sites has excellent bifunctional oxygen catalytic activity, indicating that the catalyst synthesized in the present invention has high practical application value.
进一步测试了未添加二氧化硅的电催化剂和不同Ni负载量的电催化剂的双功能氧催化活性。图7显示了Fe-NC、Ni-NC和FeNi-NC电催化剂的ORR和OER性能。双金属位点的FeNi-NC表现出明显高于Fe-NC和Ni-NC催化剂的双功能催化活性(∆E＝0.80V)，证明了Fe-Ni双原子位点的协同效应，有利于促进电子转移，加速反应动力学。而在添加了模板二氧化硅后，获得了分级多孔结构，增大了比表面积，有利于催化活性位点的暴露，使获得的FeNi-HPNC-2相较于未添加二氧化硅的双金属FeNi-NC具有更高的双功能氧活性(∆E＝0.72V)。此外，FeNi HPNC中特定的Fe/Ni摩尔比对于促进氧催化活性的ORR和OER非常重要(图8)。与FeNi-HPNC-1 (E 1/2=0.847, E j =10=0.38V)和FeNi-HPNC-3(E 1/2=0.862, E j =10=0.0.37V) 相比，Fe/Ni摩尔比为1的FeNi-HPNC-2表现出相对优异的ORR(E 1/2=0.868V)以及OER(E j =10=0.36V)活性，双功能氧活性∆E为0.72V)。 The bifunctional oxygen catalytic activity of electrocatalysts without added silica and electrocatalysts with different Ni loadings was further tested. Figure 7 shows the ORR and OER performance of Fe-NC, Ni-NC and FeNi-NC electrocatalysts. FeNi-NC at bimetallic sites showed significantly higher bifunctional catalytic activity (ΔE=0.80V) than Fe-NC and Ni-NC catalysts, proving the synergistic effect of Fe-Ni diatomic sites, which is beneficial to promoting Electron transfer accelerates reaction kinetics. After adding template silica, a hierarchical porous structure was obtained, which increased the specific surface area and was conducive to the exposure of catalytically active sites, making the obtained FeNi-HPNC-2 better than the bimetal without adding silica. FeNi-NC has higher bifunctional oxygen activity (ΔE=0.72V). Furthermore, the specific Fe/Ni molar ratio in FeNi HPNC is very important to promote the ORR and OER of oxygen catalytic activity (Figure 8). Compared with FeNi-HPNC-1 (E 1/2 =0.847, E j =10 =0.38V) and FeNi-HPNC-3 (E 1/2 =0.862, E j =10 =0.0.37V), Fe/ FeNi-HPNC-2 with a Ni molar ratio of 1 shows relatively excellent ORR (E 1/2 =0.868V) and OER (E j =10 =0.36V) activities, and the bifunctional oxygen activity ΔE is 0.72V).
催化剂在锌-空气电池中的应用：将合成的催化剂(1mg)和乙炔黑(0.25mg)分散在10µL Nafion (5 wt.%)与250µL乙醇的混合溶液中，超声处理1小时，得到浆料。将催化剂浆料以1mg·cm -2的负载量均匀的滴在碳纸上，作为锌空气电池的阴极，以打磨过的锌板作为阳极。可充电锌空气电池由空气阴极、锌阳极和含有0.2M乙酸锌的6.0 M KOH电解质构成，组装方法为常规技术。 Application of catalysts in zinc-air batteries: Disperse the synthesized catalyst (1mg) and acetylene black (0.25mg) in a mixed solution of 10µL Nafion (5 wt.%) and 250µL ethanol, and conduct ultrasonic treatment for 1 hour to obtain a slurry . The catalyst slurry was evenly dropped on the carbon paper with a loading of 1 mg·cm -2 as the cathode of the zinc-air battery, and the polished zinc plate was used as the anode. The rechargeable zinc-air battery consists of an air cathode, a zinc anode, and a 6.0 M KOH electrolyte containing 0.2 M zinc acetate. The assembly method is conventional technology.
图9为可充电锌空气电池性能测试结果。利用FeNi-HPNC-2催化剂作为空气阴极和锌阳极构建了可充电锌空气电池（ZAB），自组装ZAB的配置如图9a所示。此外，还组装了Pt/C-RuO 2作为空气阴极的催化剂以进行比较。图9b的充放电极化曲线表明，与Pt/C-RuO 2催化剂组装的ZAB相比，在300 mA cm -2的电流密度下，基于FeNi-HPNC-2的ZAB显示出较低的充电电压和较高的放电电压，且极化电压间隙较小，表明FeNi-HPNC-2具有更好的电池性能。图9c显示基于FeNi-HPNC-2的ZAB具有240 mW cm -2的最高功率密度，优于Pt/C- RuO 2 (200 mW cm −2)。图9d中，基于FeNi-HPNC-2的ZAB表现有较高的开路电压(1.48 V), 且在10mA cm -2电流密度下能持续放电超过40小时，而Pt/C-RuO 2基ZAB在放电30小时后观察到明显的电压降，表明基于FeNi-HPNC-2的ZAB更加稳定。此外，如图9e所示，基于FeNi-HPNC-2的ZAB也表现出更高的比容量(815.8 mAh g -1)，优于Pt/C-RuO 2的ZAB(713.9 mAh g -1)。不同电流密度的电池性能如图9f所示，与Pt/C-RuO 2的ZAB相比，基于FeNi-HPNC-2的ZAB显示出更高且更稳定的放电电压平台，尤其是在大电流密度下，这表明FeNi-HP-2组装的ZAB具有优异的倍率性能。通过放电30分钟和充电30分钟的循环充放电测量进一步评估ZAB的循环耐久性。图9g中显示的结果表明，基于FeNi-HPNC-2的ZABs在前几个循环中提供了0.82 V的较小充放电电位间隙(放电平台为1.16 V，充电平台为1.98 V)，以及58.6%的良好电压效率(放电电压与充电电压的比率)， 且在持续循环超过250小时，表现出优异的长期稳定性。与之相反，基于Pt/C-RuO 2的ZAB的电池只能稳定循环150小时。如图9h所示，两个基于FeNi-HPNC-2的ZABs串联，可以持续为LED灯泡显示器供电(2.5 V)，表明FeNi-HPNC-2具有潜在的商业应用前景。 Figure 9 shows the performance test results of rechargeable zinc-air batteries. A rechargeable zinc-air battery (ZAB) was constructed using FeNi-HPNC-2 catalyst as the air cathode and zinc anode. The configuration of the self-assembled ZAB is shown in Figure 9a. In addition, Pt/C- RuO2 was also assembled as a catalyst for the air cathode for comparison. The charge-discharge polarization curve in Figure 9b shows that the FeNi-HPNC- 2 based ZAB shows a lower charging voltage at a current density of 300 mA cm - 2 compared with the ZAB assembled with Pt/C-RuO2 catalyst and higher discharge voltage, and the polarization voltage gap is smaller, indicating that FeNi-HPNC-2 has better battery performance. Figure 9c shows that FeNi-HPNC-2 based ZAB has the highest power density of 240 mW cm −2 , which is better than Pt/C-RuO 2 (200 mW cm −2 ). In Figure 9d, the ZAB based on FeNi-HPNC-2 shows a higher open circuit voltage (1.48 V) and can continue to discharge for more than 40 hours at a current density of 10 mA cm -2 , while the ZAB based on Pt/C-RuO 2 An obvious voltage drop was observed after 30 hours of discharge, indicating that FeNi-HPNC-2 based ZAB is more stable. In addition, as shown in Figure 9e, the ZAB based on FeNi-HPNC-2 also exhibits a higher specific capacity (815.8 mAh g -1 ), which is better than that of Pt/C-RuO 2 (713.9 mAh g -1 ). The battery performance at different current densities is shown in Figure 9f. Compared with the ZAB of Pt/C-RuO2, the ZAB based on FeNi-HPNC- 2 shows a higher and more stable discharge voltage platform, especially at large current densities. , which indicates that the FeNi-HP-2 assembled ZAB has excellent rate performance. The cycle durability of ZAB was further evaluated through cyclic charge-discharge measurements of 30 minutes of discharge and 30 minutes of charge. The results shown in Figure 9g show that FeNi-HPNC-2-based ZABs provide a smaller charge-discharge potential gap of 0.82 V in the first few cycles (1.16 V for the discharge plateau and 1.98 V for the charge plateau), and 58.6% Good voltage efficiency (ratio of discharge voltage to charging voltage) and excellent long-term stability after continuous cycling for more than 250 hours. In contrast, the battery based on Pt/C- RuO2 ZAB can only cycle stably for 150 hours. As shown in Figure 9h, two FeNi-HPNC-2-based ZABs connected in series can continuously power an LED bulb display (2.5 V), indicating that FeNi-HPNC-2 has potential commercial applications.
XRD、Raman、BET、SEM、HAADF‑STEM、以及ORR+OER+Zn‑空气的测量结果表明：采用本发明方法所制备的铁镍双金属单原子氮掺杂多孔碳电催化剂(FeNi-HPNC)，合成方法简单、成本低廉、且具有较高的双功能氧催化活性，对于低成本双金属单原子催化剂的发展起到一定的推动作用。The measurement results of XRD, Raman, BET, SEM, HAADF-STEM, and ORR+OER+Zn-air show that: the iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst (FeNi-HPNC) prepared by the method of the present invention , the synthesis method is simple, the cost is low, and it has high bifunctional oxygen catalytic activity, which plays a certain role in promoting the development of low-cost bimetallic single-atom catalysts.
以上实施例仅为本发明较优的实施方式，仅用于解释本发明，而非限制本发明，本领域技术人员在未脱离本发明精神实质下所作的改变、替换、修饰等均应属于本发明的保护范围。The above embodiments are only preferred embodiments of the present invention and are only used to explain the present invention rather than limit the present invention. Changes, substitutions, modifications, etc. made by those skilled in the art without departing from the spirit and essence of the present invention shall all belong to this invention. protection scope of the invention.
尽管已经报道了几种基于湿化学合成方法的DAC构建方法，包括溶剂热法、MOF衍生法、竞争络合策略、双溶剂离子沉积法等，但合理设计和制造具有高催化活性的DAC仍然是一个巨大挑战。可控合成碳基体中均匀分散的双金属原子，具有可扩展性，对于DAC的应用具有重要意义。本发明首次提出的机械力化学策略被证明是一种简单有效的大规模合成高稳定性铁原子囊的方法。在这一贡献中，通过引入镍原子，本发明提出了一种技术上和经济上可行的机械力化学策略，以制备锚定在分级多孔氮掺杂碳（FeNi HPNC）上的双原子铁镍位点，通过限定控制铁镍比，具有优化的双原子铁镍位点的FeNi- HPNC对ORR和OER显示出优异的双功能催化活性。实现了0.72V的低过电位（对于ORR为E 1/2=0.868V，对于OER为E j =10=1.59V），优于单原子催化剂Fe-HPNC和Ni-HPNC，甚至大于贵金属催化剂。此外，以FeNi-HPNC为空气阴极催化剂的实用可充电锌-空气电池具有优异的功率密度和循环稳定性。 Although several DAC construction methods based on wet chemical synthesis methods have been reported, including solvothermal method, MOF derivatization method, competitive complexation strategy, dual-solvent ion deposition method, etc., the rational design and fabrication of DAC with high catalytic activity is still A huge challenge. The controllable synthesis of uniformly dispersed bimetallic atoms in the carbon matrix is scalable and is of great significance for the application of DAC. The mechanochemical strategy proposed for the first time in this invention has been proven to be a simple and effective method for large-scale synthesis of highly stable iron atom capsules. In this contribution, we propose a technically and economically feasible mechanochemical strategy to prepare diatomic iron-nickel anchored on hierarchical porous nitrogen-doped carbon (FeNi HPNC) by introducing nickel atoms. By defining the iron-nickel ratio, FeNi-HPNC with optimized diatomic iron-nickel sites shows excellent bifunctional catalytic activity for ORR and OER. A low overpotential of 0.72V (E 1/2 =0.868V for ORR and E j =10 =1.59V for OER) is achieved, which is better than single-atom catalysts Fe-HPNC and Ni-HPNC, and even larger than noble metal catalysts. In addition, a practical rechargeable zinc-air battery using FeNi-HPNC as the air cathode catalyst has excellent power density and cycle stability.

Claims (10)

  1. 一种铁镍双金属单原子氮掺杂多孔碳电催化剂的制备方法，其特征在于，包括如下步骤：将二氧化硅、氧化锌、铁盐、镍盐、二-甲基咪唑混合球磨，然后将球磨产物洗涤干燥，再碳化处理，得到铁镍双金属单原子氮掺杂多孔碳电催化剂。A method for preparing an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst, which is characterized by including the following steps: mixing and ball milling silica, zinc oxide, iron salt, nickel salt, and di-methylimidazole, and then The ball-milled product is washed, dried, and then carbonized to obtain an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst.
  2. 根据权利要求1所述铁镍双金属单原子氮掺杂多孔碳电催化剂的制备方法，其特征在于：以赖氨酸、十二烷、正硅酸乙酯为原料制备二氧化硅；所述二氧化硅为二氧化硅球，直径为10～30 nm。The preparation method of the iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst according to claim 1, characterized in that: lysine, dodecane, and ethyl orthosilicate are used as raw materials to prepare silica; Silica is a silica sphere with a diameter of 10 to 30 nm.
  3. 根据权利要求1所述铁镍双金属单原子氮掺杂多孔碳电催化剂的制备方法，其特征在于：所述铁盐为硝酸铁、镍盐为硝酸镍；氧化锌、二-甲基咪唑、铁盐、镍盐的摩尔比为 （15～20）∶（35～40）∶1∶1。The preparation method of the iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst according to claim 1, characterized in that: the iron salt is iron nitrate, the nickel salt is nickel nitrate; zinc oxide, di-methylimidazole, The molar ratio of iron salt and nickel salt is (15~20):(35~40):1:1.
  4. 根据权利要求1所述铁镍双金属单原子氮掺杂多孔碳电催化剂的制备方法，其特征在于：所述球磨的转速为800～1200 rpm，时间为150～200分钟。The preparation method of iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst according to claim 1, characterized in that: the rotation speed of the ball mill is 800-1200 rpm, and the time is 150-200 minutes.
  5. 根据权利要求1所述铁镍双金属单原子氮掺杂多孔碳电催化剂的制备方法，其特征在于：所述碳化处理是惰性气氛条件下以2～8℃·min -1的升温速率由室温加热到800～1100℃，然后持续1～4小时；碳化处理后，将碳化产物分散在HF溶液中3～8小时，然后洗涤，得到铁镍双金属单原子氮掺杂多孔碳电催化剂。 The preparation method of iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst according to claim 1, characterized in that: the carbonization treatment is carried out under inert atmosphere conditions at a heating rate of 2 to 8° C. min -1 from room temperature. Heating to 800 to 1100°C, and then continuing for 1 to 4 hours; after carbonization, the carbonization product is dispersed in HF solution for 3 to 8 hours, and then washed to obtain an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst.
  6. 根据权利要求1所述铁镍双金属单原子氮掺杂多孔碳电催化剂的制备方法制备的电催化剂，其特征在于：所述电催化剂具有分级多孔碳结构。The electrocatalyst prepared according to the preparation method of an iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst according to claim 1, characterized in that: the electrocatalyst has a hierarchical porous carbon structure.
  7. 一种可充电电池，其特征在于，所述空气电池的阴极催化剂为权利要求6所述铁镍双金属单原子氮掺杂多孔碳电催化剂。A rechargeable battery, characterized in that the cathode catalyst of the air battery is the iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst of claim 6.
  8. 权利要求6所述铁镍双金属单原子氮掺杂多孔碳电催化剂在双功能氧催化中的应用。Application of the iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst described in claim 6 in bifunctional oxygen catalysis.
  9. 权利要求6所述铁镍双金属单原子氮掺杂多孔碳电催化剂在制备锌-空气电池中的应用。Application of the iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst described in claim 6 in the preparation of zinc-air batteries.
  10. 权利要求6所述铁镍双金属单原子氮掺杂多孔碳电催化剂在提升锌-空气电池稳定性中的应用。The application of the iron-nickel bimetallic single-atom nitrogen-doped porous carbon electrocatalyst described in claim 6 in improving the stability of zinc-air batteries.
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