WO2020199368A1 - Mof化合物和非贵金属催化剂的制备方法 - Google Patents

Mof化合物和非贵金属催化剂的制备方法 Download PDF

Info

Publication number
WO2020199368A1
WO2020199368A1 PCT/CN2019/091842 CN2019091842W WO2020199368A1 WO 2020199368 A1 WO2020199368 A1 WO 2020199368A1 CN 2019091842 W CN2019091842 W CN 2019091842W WO 2020199368 A1 WO2020199368 A1 WO 2020199368A1
Authority
WO
WIPO (PCT)
Prior art keywords
mof compound
mof
compound
salt
nitrogen
Prior art date
Application number
PCT/CN2019/091842
Other languages
English (en)
French (fr)
Inventor
章潇慧
孙帮成
龚明
Original Assignee
中车工业研究院有限公司
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 中车工业研究院有限公司 filed Critical 中车工业研究院有限公司
Priority to JP2021559482A priority Critical patent/JP7253074B2/ja
Publication of WO2020199368A1 publication Critical patent/WO2020199368A1/zh

Links

Images

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22Organic complexes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9008Organic or organo-metallic compounds
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Definitions

  • This application relates to the technical field of electrocatalysts, in particular to a method for preparing MOF compounds and non-noble metal catalysts.
  • Fuel cell has the advantages of high energy density, environmental friendliness and resource saving, and has become one of the ideal energy storage devices.
  • the air electrode or the oxygen electrode undergoes complex oxygen reduction reactions and oxygen evolution reactions. These reactions require catalysts to increase the reaction rate due to poor reaction kinetics.
  • Precious metal catalysts have disadvantages such as high price, resource shortage and single catalytic performance. At present, non-precious metal catalysts are often used to increase the reaction rate.
  • zinc-based-MOF Metal-Organic Framework
  • the decomposition temperature is usually between 900°C and 1100°C. This relatively high temperature will cause the active metal centers to aggregate and form inactive structures, which will limit the synthesis efficiency and reduce the activity of the prepared non-noble metal catalysts.
  • this application provides a method for preparing MOF compounds and non-noble metal catalysts.
  • the first aspect of the present application provides a MOF compound, the self-sacrificial metal center of the MOF compound is magnesium, and the reactive site of the MOF compound includes magnesium.
  • the organic ligand of the MOF compound includes at least one of the following substances: terephthalic acid or triethylene diamine.
  • the reactive sites of the MOF compound further include any one of the following substances: iron, cobalt or nickel.
  • the second aspect of the present application provides a method for preparing the MOF compound as provided in the first aspect of the present application, and the method includes:
  • the metal salt and the organic ligand are uniformly mixed in an organic solvent to obtain a mixture;
  • the metal salt includes a magnesium salt;
  • the reaction product is washed and vacuum dried to obtain the MOF compound.
  • the mixture is reacted at a first specified temperature range of 100°C to 170°C.
  • reaction time of the reaction ranges from 1 h to 3 h.
  • the metal salt also includes any one of the following substances: iron salt, cobalt salt or nickel salt.
  • the organic ligand includes at least one of the following substances: terephthalic acid or triethylene diamine.
  • the metal salt includes Mg(NO 3 ) 2 ⁇ 6H 2 O and Fe(NO 3 ) 3 ⁇ 9H 2 O.
  • the third aspect of the present application provides a method for preparing a non-noble metal catalyst using any MOF compound as provided in the first aspect of the present application, and the method includes:
  • the mixed powder is pyrolyzed to obtain a non-precious metal catalyst.
  • the mixed powder is pyrolyzed in a temperature range of 700°C to 1200°C.
  • the pyrolysis time of the pyrolysis ranges from 10 min to 60 min.
  • the mass ratio of the MOF compound to the nitrogen-containing additive is 2:1 to 5:1.
  • the nitrogen-containing additive is o-phenanthroline.
  • the self-sacrificial metal center of MOF compound is magnesium
  • the reactive sites include magnesium
  • the boiling point of magnesium is 1089°C.
  • residual magnesium will be limited
  • the aggregation of active metal centers enables more single-atom sites to be trapped in the graphitic carbon, so that the activity of the prepared non-noble metal catalyst can be improved.
  • Fig. 1 is an XRD pattern of a MOF compound shown in an exemplary embodiment of the application
  • Figure 2 is an SEM image of a MOF compound shown in an exemplary embodiment of the application
  • Figure 3 is a flow chart of a method for preparing MOF compounds provided by an exemplary embodiment of the application.
  • Fig. 4 is a flow chart of preparing a non-noble metal catalyst provided by an exemplary embodiment of the application
  • Fig. 5 is a TEM image of a non-noble metal catalyst shown in an exemplary embodiment of the application
  • Figure 6 is the linear sweep voltammetry curve of the non-noble metal catalyst prepared in Experiment 1 in 0.1M HClO 4 solution;
  • Figure 7 shows the linear sweep voltammetry curve of the non-noble metal catalyst prepared in Experiment 2 in a 0.1M HClO 4 solution.
  • first, second, third, etc. may be used in this application to describe various information, the information should not be limited to these terms. These terms are only used to distinguish the same type of information from each other.
  • first information may also be referred to as second information, and similarly, the second information may also be referred to as first information.
  • word “if” as used herein can be interpreted as "when” or “when” or "in response to determination”.
  • This application provides a method for preparing a MOF (Metal-Organic Framework) compound and a non-noble metal catalyst, in order to reduce the agglomeration of active metal centers and prepare a non-noble metal catalyst with higher activity.
  • MOF Metal-Organic Framework
  • the first aspect of the present application provides a MOF compound, the self-sacrificial metal center of the MOF compound is magnesium, and the reactive site includes magnesium.
  • the boiling point of metallic magnesium is 1089°C
  • the self-sacrificial metal center of the MOF compound is metallic magnesium
  • the reactive sites include metallic magnesium. If the pyrolysis of the MOF compound is used to prepare a non-precious metal catalyst, the material’s The degree of graphitization is already high, and the remaining magnesium will limit the aggregation of active metal centers, so that more single-atom sites are trapped in the graphitic carbon, which can improve the activity of the prepared non-noble metal catalysts.
  • the organic ligand of the MOF compound includes at least one of the following substances: terephthalic acid (TPA) or triethylenediamine (DABCO).
  • TPA terephthalic acid
  • DABCO triethylenediamine
  • the MOF compound is a single organic ligand compound, and the single organic ligand is terephthalic acid or triethylenediamine.
  • the MOF compound is a dual organic ligand compound, and the dual organic ligand is terephthalic acid and triethylene diamine.
  • MOF compounds are organic-inorganic hybrid materials with intramolecular voids formed by coordination assembly of organic ligands and metal ions or clusters.
  • metal atoms and organic ligands are highly dispersed.
  • the reactive sites of the MOF compound further include any one of the following substances: iron, cobalt or nickel.
  • the self-sacrificial metal center of the MOF compound is magnesium
  • the reactive site includes magnesium
  • the reactive site of the MOF compound also includes iron
  • the organic ligand of the MOF compound is a double ligand (including terephthalic acid).
  • triethylenediamine as an example.
  • the MOF compound can be expressed as Mg-Fe-DABCO-TPA.
  • Figure 1 is an X-ray diffraction (XRD) image of a MOF compound shown in an exemplary embodiment of the application, which can clearly analyze the structure of MOFs;
  • Figure 2 is an SEM image of a MOF compound shown in an exemplary embodiment of the application, which can be observed To the typical morphology of MOFs.
  • XRD X-ray diffraction
  • FIG. 3 is a flowchart of the preparation method of the MOF compound provided in an embodiment of the application. Referring to Figure 3, the method may include:
  • the metal salt and the organic ligand are uniformly mixed in an organic solvent to obtain a mixture; the metal salt includes a magnesium salt.
  • the magnesium salt may be a nitrate salt.
  • the magnesium salt is Mg(NO 3 ) 2 ⁇ 6H 2 O.
  • the organic ligand includes at least one of the following substances: terephthalic acid or triethylene diamine.
  • the organic solvent may be N,N-dimethylformamide (DMF).
  • the metal salt may also include any one of the following substances: iron salt, cobalt salt or nickel salt.
  • the metal salt includes magnesium salt (for example, Mg(NO 3 ) 2 ⁇ 6H 2 O) and iron salt (for example, Fe(NO 3 ) 3 ⁇ 9H 2 O) as an example for description.
  • magnesium salt for example, Mg(NO 3 ) 2 ⁇ 6H 2 O
  • iron salt for example, Fe(NO 3 ) 3 ⁇ 9H 2 O
  • the mixture can be reacted in an oil bath, and cooled after the reaction is completed (for example, the system is opened to volatilize the organic solvent) to obtain a reaction product.
  • the above mixture is reacted at a first specified temperature range of 100° C. to 170° C.; the reaction time of the reaction ranges from 1 h to 3 h.
  • the reaction product can be washed with DMF and ethanol, filtered, and dried in vacuum to obtain the MOF compound.
  • the temperature of vacuum drying may be 60°C to 90°C.
  • the temperature of vacuum drying is 80°C.
  • the method may include: adding 15 mL of DMF into a three-necked flask and heating to 150°C, and then adding Mg(NO 3 ) 2 ⁇ 6H 2 O, Fe(NO 3 ) 3 ⁇ 9H 2 O and triethylenediamine to the three-necked flask Dissolve terephthalic acid in a beaker containing 10mL DMF at 150°C; transfer the solution in the beaker to a three-necked flask; and clean the beaker with 10mL DMF and transfer the 10mL DMF to the three-necked flask , The mixture was obtained; the mixture was stirred at a speed of 300 rpm and placed on an aluminum boat preheated to 150 °C, while the two side flask openings of the three-necked flask were sealed with glass stoppers, and the center of the three-necked flask was opened Connect to a
  • FIG. 4 is a flow chart for preparing a non-precious metal catalyst provided by an embodiment of the application. Please refer to FIG. 4, the method includes the following steps:
  • MOF compounds are used as the precursors of non-noble metal catalysts.
  • the main reasons for its use as a precursor are: (1) In a highly ordered structure, it contains all necessary catalyst components (active metal centers, carbon and nitrogen); (2) In MOF compounds, metal atoms are highly dispersed The structure is beneficial to inhibit the agglomeration of metal particles during high-temperature heat treatment.
  • the introduction of nitrogen-containing additives can increase the anchor location of the active metal in the carbon framework, and further increase the active site.
  • a ball milling method may be used to physically mix the MOF compound and the nitrogen-containing additive to obtain a mixed powder.
  • the reactants can be ball-milled and collided at a high speed in a planetary ball mill, so that nitrogen-containing additives are incorporated into the MOF compound to obtain a mixed powder.
  • a solvent method may be used to mix the MOF compound and the nitrogen-containing additive, and the mixture is dried to obtain a mixed powder.
  • DMF is used as a solvent to make the MOF compound and the nitrogen-containing additive uniformly mixed under a homogeneous condition, and then the mixture is subjected to ultrasonic treatment, centrifuged and dried to obtain a mixed powder.
  • the MOF compound and nitrogen-containing additive are mixed in 35 mL DMF at a mass ratio of 4:1 using DMF as a dispersant, ultrasonicated for 1 hour, and then centrifuged, and the resulting sample is vacuum dried at 80°C 6h, get mixed powder.
  • the solvent method can minimize the damage to the MOF compound during the ball milling process.
  • the nitrogen-containing additive may be any one of the following substances: o-phenanthroline, polyvinylpyrrolidone (PVP) or melamine.
  • o-phenanthroline when used as a nitrogen-containing additive, it helps to promote the increase of the content of pyridine nitrogen in the catalyst, increase the number of N atoms coordinated with the active center, and produce highly active substances.
  • PVP is a kind of high molecular organic polymer. When it is used as a nitrogen-containing additive, after coating the MOF compound, it can interact with the inner layer to form a dense structure. During the pyrolysis process, it is restricted by the interaction with the metal The sintering of active metal centers will limit the formation of large-sized inactive nanoparticles, thereby increasing the density of active sites.
  • the nitrogen content in melamine is very high. When used as a nitrogen-containing additive, it is easily incorporated into the carbon skeleton during the pyrolysis process to generate carbon nitride, thereby increasing the proportion of nitrogen doping in the final product and providing more metal Anchor point.
  • S402 Pyrolyze the mixed powder under an ammonia atmosphere to obtain a non-precious metal catalyst.
  • FIG. 5 is a TEM image of a non-noble metal catalyst shown in an exemplary embodiment of this application. Please refer to Figure 5. As can be seen from Figure 5, the metal particles are highly dispersed on the MOF framework.
  • the above-mentioned mixed powder is rapidly pyrolyzed under an ammonia atmosphere to obtain a non-noble metal catalyst.
  • the tube furnace before putting the mixed powder into the tube furnace, the tube furnace can be preheated to the required temperature in advance, and ammonia gas is continuously introduced into the quartz tube. Furthermore, when the temperature of the tube furnace reaches the required temperature, the sample is placed in the tube furnace for 15 minutes of reaction, and then taken out, cooled naturally to obtain a non-precious metal catalyst.
  • the above-mentioned mixed powder is rapidly pyrolyzed in a second specified temperature range of 700°C to 1200°C.
  • the second specified temperature is 1100°C.
  • the pyrolysis time range of the pyrolysis is 10 min to 60 min.
  • the pyrolysis time of the pyrolysis is 15 minutes.
  • the mass ratio of the MOF compound to the nitrogen-containing additive ranges from 2:1 to 5:1.
  • the mass ratio of the MOF compound to the nitrogen-containing additive is 4:1.
  • the activity of the non-noble metal Pt-free catalyst is characterized by a three-electrode electrochemical test under acidic conditions, and the two parameters of the starting point and the half-wave potential are used to evaluate the non-noble metal Pt-free catalyst activity. active.
  • the initial potential represents the open circuit potential of the system, that is, the potential at which the current density of the reaction system is zero; the first method to calculate this parameter is to use the potential at the limit current density of 5%; The second method is to interpolate the positive oxidation current and the negative reduction current as the intersection line, and the intersection point of the intersection line and the zero current point is the starting potential point.
  • the half-wave potential refers to the potential of the system when the current density reaches half of the limiting current density, that is, the potential at which the system current is 50% of the limiting current density.
  • the linear sweep voltammetry curve of the non-noble metal catalyst in the HClO 4 solution is obtained by the following method, which includes: placing 5 mg of the non-noble metal catalyst, 235 ⁇ L of deionized water, 235 ⁇ L of ethanol and 45 ⁇ L of electrolyte in a container In the process, a mixture is formed; the above mixture is sonicated for 30 minutes to mix the above mixture uniformly; 20 ⁇ L of the mixture is deposited on a glassy carbon electrode with an area of 0.196 cm 2 . Finally, a three-electrode battery device was used to test the electrochemical performance.
  • the reference electrode is calibrated in a HClO 4 solution; further, in a 0.1M HClO 4 solution, a linear sweep voltammetry is run at a sweep rate of 0.01V/s between 0V and 1.1V The method is to activate the catalyst; then, the gradient voltammetry is run between 1.1V and 0V at a scan rate of 0.02V/s. It should be noted that before measuring the current, the potential of each step must be maintained for 30 seconds. In addition, for all test tasks, the working electrode is rotated at 900 rpm. In this way, the starting potential can be determined by determining the potential when the current density is zero, and the half-wave potential can be determined by calculating the potential when the current density is half of the limiting current density.
  • the mixed powders are rapidly pyrolyzed at 950°C for 15 minutes to obtain non-precious metal catalysts.
  • the MOF compound is Fe-Mg-DABCO-TPA and the nitrogen-containing additive is o-phenanthroline as an example.
  • Fig. 6 is a linear sweep voltammetry curve of the non-noble metal catalyst prepared in Experiment 1 in a 0.1M HClO 4 solution. It can be seen from Fig. 6 that the starting potential is 0.82V, the half-slope potential is 0.52V, and the catalytic activity is better.
  • the MOF compound is Fe-Mg-DABCO-TPA and the nitrogen-containing additive is o-phenanthroline as an example.
  • Fig. 7 is a linear sweep voltammetry curve of the non-noble metal catalyst prepared in Experiment 2 in a 0.1M HClO 4 solution. It can be seen from Fig. 7 that the starting potential is 0.80V and the half-slope potential is 0.38V, and the catalytic activity is better. Further, please refer to FIG. 6 and FIG. 7 at the same time. It can be seen that the non-noble metal catalyst prepared at 1100° C. has a lower initial potential and half slope potential.
  • the organic ligand of the MOF compound is a dual ligand
  • the dual ligand MOF compound has a competitive relationship during the formation process, and can form MOF compounds with different coordination structures.
  • DABCO can coordinate with a metal ligand in a vertical plane to form a one-dimensional structure.
  • TPA can coordinate with the metal ligand in a horizontal plane at different angles to form a two-dimensional structure.
  • the coordination structure of the MOF compound can be controlled by precisely adjusting the ratio between organic ligands, the ratio of active species can be increased, and the density of active sites can be increased.
  • non-noble metal catalysts prepared by dual-ligand MOF compounds have better catalytic performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Inert Electrodes (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

本申请提供一种MOF化合物和非贵金属催化剂的制备方法。所述MOF化合物的自牺牲金属中心为镁且反应活性位点包括镁。

Description

MOF化合物和非贵金属催化剂的制备方法 技术领域
本申请涉及电催化剂技术领域,尤其涉及一种MOF化合物和非贵金属催化剂的制备方法。
背景技术
燃料电池具有能量密度较高、环境友好和节约资源等优点,已成为理想的储能设备之一。空气电极或氧电极作为燃料电池的主要反应场所,发生着复杂的氧还原反应和氧析出反应,这些反应因反应动力学性能较差需要借助催化剂提升反应速率。贵金属催化剂存在价格昂贵、资源短缺和催化性能单一等缺点,目前,常采用非贵金属催化剂来提升反应速率。
相关技术中常采用锌基-MOF(Metal-Organic Framework,金属-有机骨架)化合物来制备非贵金属催化剂,然而,由于锌的沸点为907℃,而在利用锌基-MOF化合物制备非贵金属催化剂时热解温度通常在900℃至1100℃之间,这一相对较高的温度会导致活性金属中心聚集并形成非活性结构,这会限制合成效率并降低制得的非贵金属催化剂的活性。
发明内容
有鉴于此,本申请提供一种MOF化合物和非贵金属催化剂的制备方法。
本申请第一方面提供一种MOF化合物,所述MOF化合物的自牺牲金属中心为镁,所述MOF化合物的反应活性位点包括镁。
进一步地,所述MOF化合物的有机配体包含以下至少一种物质:对苯二甲酸或三乙烯二胺。
进一步地,所述MOF化合物的反应活性位点还包括以下任一种物质:铁、钴或镍。
本申请第二方面提供一种如本申请第一方面提供的MOF化合物的制备方法,所述方法包括:
将金属盐、有机配体在有机溶剂中均匀混合,得到混合物;所述金属盐包括镁盐;
使所述混合物反应,得到反应产物;
对所述反应产物进行洗涤、真空干燥,得到所述MOF化合物。
进一步地,使所述混合物在100℃至170℃的第一指定温度范围反应。
进一步地,所述反应的反应时间范围为1h至3h。
进一步地,所述金属盐还包括以下任一种物质:铁盐、钴盐或镍盐。
进一步地,所述有机配体包含以下至少一种物质:对苯二甲酸或三乙烯二胺。
进一步地,所述金属盐包括Mg(NO 3) 2·6H 2O和Fe(NO 3) 3·9H 2O。
本申请第三方面提供一种利用如本申请第一方面提供的任一MOF化合物制备非贵金属催化剂的方法,所述方法包括:
将所述MOF化合物与含氮添加剂混合,得到混合粉末;
在氨气气氛下,将所述混合粉末热解,得到非贵金属催化剂。
进一步地,将所述混合粉末在700℃至1200℃的温度范围热解。
进一步地,所述热解的热解时间范围为10min至60min。
进一步地,所述MOF化合物与所述含氮添加剂的质量比为2:1至5:1。
进一步地,所述含氮添加剂为邻菲罗啉。
本申请提供的MOF化合物和非贵金属催化剂的制备方法,由于MOF化合物的自牺牲金属中心为镁,反应活性位点包括镁,而镁的沸点为1089℃,高温热解时,残留的镁会限制活性金属中心的聚集,使得更多的单原子位点被捕获在石墨碳中,这样,可提高制备的非贵金属催化剂的活性。
附图说明
图1为本申请一示例性实施例示出的MOF化合物的XRD图;
图2为本申请一示例性实施例示出的MOF化合物的SEM图;
图3为本申请一示例性实施例提供的MOF化合物制备方法的流程图;
图4为本申请一示例性实施例提供的制备非贵金属催化剂的流程图;
图5为本申请一示例性实施例示出的非贵金属催化剂的TEM图;
图6为试验一制得的非贵金属催化剂在0.1M HClO 4溶液中的线性扫描伏安曲线;
图7为试验二制得的非贵金属催化剂在0.1M HClO 4溶液中的线性扫描伏安曲线。
具体实施方式
这里将详细地对示例性实施例进行说明,其示例表示在附图中。下面的描述涉及附图时,除非另有表示,不同附图中的相同数字表示相同或相似的要素。以下示例性实施例中所描述的实施方式并不代表与本申请相一致的所有实施方式。相反,它们仅是与如所附权利要求书中所详述的、本申请的一些方面相一致的装置和方法的例子。
在本申请使用的术语是仅仅出于描述特定实施例的目的,而非旨在限制本申请。在本申请和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式,除非上下文清楚地表示其他含义。还应当理解,本文中使用的术语“和/或”是指并包含一个或多个相关联的列出项目的任何或所有可能组合。
应当理解,尽管在本申请可能采用术语第一、第二、第三等来描述各种信息,但这些信息不应限于这些术语。这些术语仅用来将同一类型的信息彼此区分开。例如,在不脱离本申请范围的情况下,第一信息也可以被称为第二信息,类似地,第二信息也可以被称为第一信息。取决于语境,如在此所使用的词语“如果”可以被解释成为“在……时”或“当……时”或“响应于确定”。
本申请提供一种MOF(Metal-Organic Framework,金属-有机骨架)化合物和非贵金属催化剂的制备方法,以期降低活性金属中心的团聚,制备出活性较高的非贵金属催化剂。
下面给出几个具体的实施例,用以详细说明本申请提供的MOF化合物、MOF化合物的制备方法和非贵金属催化剂的制备方法。下面这几个具体的实施例可以相互结合,对于相同或相似的概念或过程,可能在某些实施例中不再赘述。
本申请第一方面提供一种MOF化合物,所述MOF化合物的自牺牲金属中心为镁,反应活性位点包括镁。
具体的,金属镁的沸点为1089℃,MOF化合物的自牺牲金属中心为金属镁,反应活性位点包括金属镁时,若利用MOF化合物热解制备非贵金属催化剂,在金属镁蒸发之前,材料的石墨化程度已经很高,残留的镁会限制活性金属中心的聚集,使得更多的单原子位点被捕获在石墨碳中,这样,可提高制备的非贵金属催化剂的活性。
可选地,所述MOF化合物的有机配体包含以下至少一种物质:对苯二甲酸(TPA)或三乙烯二胺(DABCO)。
例如,一实施例中,该MOF化合物为单有机配体化合物,该单有机配体为对苯二甲酸或三乙烯二胺。再例如,另一实施例中,该MOF化合物为双有机配体化合物,该双有机配体为对苯二甲酸和三乙烯二胺。
需要说明的是,MOF化合物是由有机配体和金属离子或团簇通过配位组装形成的具有分子内空隙的有机-无机杂化材料。MOF化合物中,金属原子以及有机配体高度分散。
可选地,所述MOF化合物的反应活性位点还包括以下任一种物质:铁、钴或镍。
下面以MOF化合物的自牺牲金属中心为镁,反应活性位点包括镁,且该MOF化合物的反应活性位点还包括铁,以及该MOF化合物的有机配体为双配体(包含对苯二甲酸和三乙烯二胺)为例进行说明。具体的,本例中,该MOF化合物可以表示为Mg-Fe-DABCO-TPA。
图1为本申请一示例性实施例示出的MOF化合物的X射线衍射(XRD)图,可清楚解析出MOFs结构;图2为本申请一示例性实施例示出的MOF化合物的SEM图,可观察到典型的MOFs形貌。
下面介绍一下MOF化合物的制备方法,图3为本申请一实施例提供的MOF化合物制备方法的流程图。请参照图3,该方法可以包括:
S301、将金属盐、有机配体在有机溶剂中均匀混合,得到混合物;所述金属盐包括镁盐。
具体的,该镁盐可以为硝酸盐,例如,一实施例中,该镁盐为Mg(NO 3) 2·6H 2O。进一步地,有机配体包含以下至少一种物质:对苯二甲酸或三乙烯二胺。需要说明的是,有机溶剂可以是N,N-二甲基甲酰胺(DMF)。
可选地,一实施例中,该金属盐还可以包括以下任一种物质:铁盐、钴盐或镍盐。
下面以金属盐包括镁盐(例如,可以是Mg(NO 3) 2·6H 2O)和铁盐(例如,可以是Fe(NO 3) 3·9H 2O)为例进行说明。本步骤中,将镁盐、铁盐、有机配体在DMF中均匀混合,得到混合物。
S302、使上述混合物反应,得到反应产物。
具体的,可使混合物在油浴中反应,在反应完成后冷却(例如,敞开体系挥发有机 溶剂),从而得到反应产物。
S303、对上述反应产物进行洗涤、真空干燥,得到MOF化合物。
具体的,使上述混合物在100℃至170℃的第一指定温度范围反应;所述反应的反应时间范围为1h至3h。
具体的,反应产物可经DMF和乙醇洗涤后过滤,真空干燥得到MOF化合物。需要说明的是,真空干燥的温度可以为60℃至90℃,例如,一实施例中,真空干燥的温度为80℃。
下面给出一个具体的例子,用于详细说明制备MOF化合物的方法。该方法可以包括:将15mL DMF加入三颈瓶中并加热至150℃,然后将Mg(NO 3) 2·6H 2O、Fe(NO 3) 3·9H 2O和三乙烯二胺加入三颈瓶中;将对苯二甲酸溶解于盛有150℃、10mL DMF的烧杯中;将烧杯中的溶液转移到三颈瓶中;并用10mL DMF清洗烧杯后将该10mL DMF也转移到三颈瓶中,得到混合物;将混合物以300转/分的速度搅拌并置于预热至150℃的铝舟上,同时用玻璃塞密封三颈瓶的两个侧烧瓶开口,并将三颈瓶的中心开口连接到通有冷水的冷凝器上以防止DMF蒸发;反应2小时,停止加热及搅拌,之后除去一个玻璃塞和冷凝器,以使DMF缓慢蒸发;DMF蒸发完全后,将反应产物用热DMF洗涤,并在80℃下真空干燥,进而得到MOF化合物。
下面介绍本申请提供的利用上述MOF化合物制备非贵金属催化剂的方法:
具体的,图4为本申请一实施例提供的制备非贵金属催化剂的流程图,请参照图4,所述方法包括以下步骤:
S401、将所述MOF化合物与含氮添加剂混合,得到混合粉末。
具体的,本申请中,采用MOF化合物作为非贵金属催化剂的前驱体。其作为前驱体的主要原因有:(1)在高度有序的结构中,包含所有必须的催化剂组分(活性金属中心、碳和氮);(2)在MOF化合物中,金属原子高度分散的结构有利于抑制高温热处理过程中金属颗粒的团聚。此外,含氮添加剂的引入,可提高碳骨架中活性金属的锚定位点,进一步提高活性位点。
具体的,在一种实现方式中,可使用球磨法将MOF化合物与含氮添加剂物理混合,得到混合粉末。有关球磨法的具体操作步骤可以参见相关技术中的描述,此处不再赘述。例如,可将反应物在行星式球磨机中高速球磨碰撞,使得含氮添加剂掺入MOF化合物中,得到混合粉末。
在另一种实现方式中,可使用溶剂法将MOF化合物与含氮添加剂混合,并干燥混合物,得到混合粉末。本实现方式中,主要通过DMF作为溶剂使得MOF化合物与含氮添加剂在均相条件下混合均匀,进而对混合物进行超声处理后离心分离并干燥,得到混合粉末。例如,一实施例中,通过DMF作为分散剂将MOF化合物和含氮添加剂在35mL DMF中以4:1的质量比混合并超声处理1小时后离心分离,进而将所得样品在80℃下真空干燥6h,得到混合粉末。
需要说明的是,溶剂法与球磨法相比,可最大限度地减少球磨过程中对MOF化合物造成的破坏。
进一步地,含氮添加剂可以为下述物质中的任意一种:邻菲罗啉、聚乙烯吡咯烷酮(PVP)或三聚氰胺。
具体的,邻菲罗啉作为含氮添加剂时,有助于促进催化剂中吡啶氮的含量升高,增加与活性中心配位的N原子的数量,产生高活性的物质。
PVP作为一种高分子有机聚合物,其作为含氮添加剂时,在包覆MOF化合物后,可以与内层相互作用形成一层致密的结构,在热解过程中,通过与金属的相互作用限制活性金属中心的烧结,这将限制大尺寸的非活性纳米颗粒形成,从而可提高活性位点的密度。
三聚氰胺中的氮含量非常高,当其作为含氮添加剂时,在热解过程中,容易掺入碳骨架中,生成氮化碳,从而增加最终产物中氮掺杂的比例,提供更多的金属锚定位点。
S402、在氨气气氛下,使所述混合粉末热解,得到非贵金属催化剂。
需要说明的是,在热解的过程中,MOF化合物的骨架结构得以保留,且金属原子不易团聚,能够产生高度分散的金属原子活性位点。
例如,图5为本申请一示例性实施例示出的非贵金属催化剂的TEM图。请参照图5,从图5中可以看出,金属颗粒高度分散于MOF骨架上。
具体的,本步骤中,在氨气气氛下,使上述混合粉末快速热解,得到非贵金属催化剂。具体实现时,在将混合粉末放入管式炉之前,可提前将管式炉预热到所需温度,石英管中持续通入氨气。进而在管式炉温度达到所需温度时,将样品放入管式炉中反应15min后取出,自然冷却,得到非贵金属催化剂。
可选地,使上述混合粉末在700℃至1200℃的第二指定温度范围快速热解,例如, 在一实现方式中,第二指定温度为1100℃。所述热解的热解时间范围为10min至60min。例如在一实现方式中,所述热解的热解时间为15min。此外,所述MOF化合物与含氮添加剂的质量比范围为2:1至5:1。例如,在一实现方式中,所述MOF化合物与含氮添加剂的质量比为4:1。
需要说明的是,本申请中,在酸性条件下通过三电极电化学测试对非贵金属无Pt催化剂的活性进行表征,以起始点位和半波电位这两个参数来评估非贵金属无Pt催化剂的活性。此外,起始电位,表征体系的开路电位,也就是反应体系电流密度为0时所处的电位;计算这一参数的第一种方法是采用百分之五的极限电流密度所处的电位;第二种方法则是将正氧化电流和负还原电流进行插值做交线,交线与零电流点的交点即为起始电位点。进一步地,半波电位指的是当电流密度达到极限电流密度一半时体系的电位,即当体系电流为极限电流密度的50%时所处的电位。
例如,一实施例中,非贵金属催化剂在HClO 4溶液中的线性扫描伏安曲线采用如下方法测试获得,该方法包括:将5mg非贵金属催化剂、235μL去离子水、235μL乙醇和45μL电解质置于容器中,形成混合物;将上述混合物超声处理30min,以将上述混合物混合均匀;将20μL混合物沉积在一个面积为0.196cm 2的玻璃碳电极上。最后,用三电极电池装置测试电化学性能。
具体的,在测试开始前,将参比电极在HClO 4溶液中校准;进一步地,在0.1M HClO 4溶液中,以0.01V/s的扫描速率在0V至1.1V之间运行线性扫描伏安法,以激活催化剂;接着,以0.02V/s的扫描速率,在1.1V到0V之间运行梯度伏安法。需要说明的是,在测量电流前,每个步骤的电位需保持30秒,此外,对于所有测试工作,工作电极均以900rpm旋转。这样,即可通过确定电流密度为0时的电位来确定起始电位,并通过计算极限电流密度的一半时的电位来确定半波电位。
下面给出几个具体的实施例,用于详细介绍非贵金属催化剂的制备方法:
试验一
(1)将质量比为4:1的MOF化合物和含氮添加剂通过球磨法物理混合,得到混合粉末;
(2)在氨气气氛下,将混合粉末分别在950℃下快速热解15min,得到非贵金属催化剂。
具体的,本例中,以MOF化合物为Fe-Mg-DABCO-TPA,含氮添加剂为邻菲罗啉 为例进行说明。进一步地,图6为试验一制得的非贵金属催化剂在0.1M HClO 4溶液中的线性扫描伏安曲线。从图6中可以看出,起始电位为0.82V,半坡电位为0.52V,催化活性较好。
试验二
(1)将质量比为4:1的MOF化合物和含氮添加剂通过球磨法物理混合,得到混合粉末
(2)在氨气气氛下,将混合粉末分别在1100℃下快速热解15min,得到非贵金属催化剂。
具体的,本例中,仍以MOF化合物为Fe-Mg-DABCO-TPA,含氮添加剂为邻菲罗啉为例进行说明。
进一步地,图7为试验二制得的非贵金属催化剂在0.1M HClO 4溶液中的线性扫描伏安曲线。从图7中可以看出,起始电位为0.80V,半坡电位为0.38V,催化活性较好。进一步地,请同时参照图6和图7,可知,1100℃下制得的非贵金属催化剂具有更低的起始电位和半坡电位。
需要说明的是,当MOF化合物的有机配体为双配体时,双配体MOF化合物在形成过程中存在竞争关系,可以形成不同配位结构的MOF化合物。例如,DABCO作为含氮配体,可以与金属配体在垂直平面配位,形成一维结构。TPA作为含氧配体,可以与金属配体以不同角度在水平平面内配位,形成二维结构。
具体的,可以通过精确调控有机配体之间的比例,控制MOF化合物的配位结构,提高活性物种的比例,增加活性位点的密度。
进一步地,相比于单配体MOF化合物,通过双配体MOF化合物制得的非贵金属催化剂催化性能更好。
在不产生冲突的情况下,本申请上述各实施方式或实施例的内容可以互为补充。
以上所述仅为本申请的较佳实施例而已,并不用以限制本申请,凡在本申请的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本申请保护的范围之内。

Claims (14)

  1. 一种金属有机骨架MOF化合物,所述MOF化合物的自牺牲金属中心为镁且所述MOF化合物的反应活性位点包括镁。
  2. 根据权利要求1所述的方法,所述MOF化合物的有机配体包含以下至少一种物质:对苯二甲酸或三乙烯二胺。
  3. 根据权利要求1所述的方法,所述MOF化合物的反应活性位点还包括以下任一种物质:铁、钴或镍。
  4. 一种如权利要求1所述MOF化合物的制备方法,包括:
    将金属盐、有机配体在有机溶剂中均匀混合,得到混合物;所述金属盐包括镁盐;
    使所述混合物反应,得到反应产物;
    对所述反应产物进行洗涤、真空干燥,得到所述MOF化合物。
  5. 根据权利要求4所述的方法,使所述混合物在100℃至170℃的第一指定温度范围反应。
  6. 根据权利要求4所述的方法,所述反应的反应时间范围为1h至3h。
  7. 根据权利要求4所述的方法,所述金属盐还包括以下任一种物质:铁盐、钴盐或镍盐。
  8. 根据权利要求4所述的方法,所述有机配体包含以下至少一种物质:对苯二甲酸或三乙烯二胺。
  9. 根据权利要求7所述的方法,所述金属盐包括Mg(NO 3) 2·6H 2O和Fe(NO 3) 3·9H 2O。
  10. 一种利用如权利要求1-3中任一项所述MOF化合物制备非贵金属催化剂的方法,包括:
    将所述MOF化合物与含氮添加剂混合,得到混合粉末;
    在氨气气氛下,使所述混合粉末热解,得到非贵金属催化剂。
  11. 根据权利要求10所述的方法,使所述混合粉末在700℃至1200℃的第二指定温度范围热解。
  12. 根据权利要求10所述的方法,所述热解的热解时间范围为10min至60min。
  13. 根据权利要求10所述的方法,所述MOF化合物与所述含氮添加剂的质量比范围为2:1至5:1。
  14. 根据权利要求10所述的方法,所述含氮添加剂为邻菲罗啉。
PCT/CN2019/091842 2019-04-02 2019-06-19 Mof化合物和非贵金属催化剂的制备方法 WO2020199368A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021559482A JP7253074B2 (ja) 2019-04-02 2019-06-19 Mof化合物と非貴金属触媒の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910261121.4A CN111769294B (zh) 2019-04-02 2019-04-02 Mof化合物和非贵金属催化剂的制备方法
CN201910261121.4 2019-04-02

Publications (1)

Publication Number Publication Date
WO2020199368A1 true WO2020199368A1 (zh) 2020-10-08

Family

ID=72664890

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/091842 WO2020199368A1 (zh) 2019-04-02 2019-06-19 Mof化合物和非贵金属催化剂的制备方法

Country Status (3)

Country Link
JP (1) JP7253074B2 (zh)
CN (1) CN111769294B (zh)
WO (1) WO2020199368A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113172234A (zh) * 2021-04-13 2021-07-27 南开大学 一种碳基单原子电催化剂的制备方法
CN113262810A (zh) * 2021-06-09 2021-08-17 四川大学 一种单原子催化剂m-sac及其制备方法和用途
CN114425365A (zh) * 2022-01-29 2022-05-03 重庆交通大学 富缺陷Mn-Co金属氧化物催化剂的制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113019352A (zh) * 2021-03-16 2021-06-25 山东建筑大学 一种嵌入式碱土金属氧化物固体碱的制备方法及其在生物柴油生产中的应用
US11986814B2 (en) 2021-03-16 2024-05-21 Shandong Jianzhu University Preparation method of embedded alkaline earth metal oxide solid alkali and application thereof in biodiesel production
CN114292413B (zh) * 2021-12-31 2023-10-27 贵州乌江水电开发有限责任公司思林发电厂 一种基于芳香羧酸类MOFs的自修复材料制备方法及应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103992339A (zh) * 2014-05-21 2014-08-20 哈尔滨工业大学 合成金属有机框架物材料Mg-MOF-74的方法
US20160211545A1 (en) * 2012-08-10 2016-07-21 The Regents Of The University Of California Solid lithium electrolyte via addition of lithium salts to metal-organic frameworks
CN107759801A (zh) * 2017-09-27 2018-03-06 华南理工大学 利用晶体缺陷法合成中微双孔mof‑74材料的方法
CN107949941A (zh) * 2015-09-08 2018-04-20 庄信万丰燃料电池有限公司 氧气还原反应催化剂
US20180226682A1 (en) * 2017-02-07 2018-08-09 University Of California, Los Angeles Composite electrolyte membrane, fabrication methods and applications of same
CN109316978A (zh) * 2018-10-25 2019-02-12 上海科技大学 一种MOFs材料及其制备方法和用途
CN109638304A (zh) * 2018-12-29 2019-04-16 江苏大学 一种m-mof-74/石墨烯复合阴极材料的制备方法和用途

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE502007001918D1 (de) 2006-05-16 2009-12-17 Basf Se Verfahren zur herstellung von porösen metallorganischen gerüstmaterialien
ES2713194T3 (es) 2007-09-25 2019-05-20 Univ California Entramados organometálicos comestibles y biocompatibles
US8876953B2 (en) * 2009-06-19 2014-11-04 The Regents Of The University Of California Carbon dioxide capture and storage using open frameworks
JP2014004519A (ja) 2012-06-22 2014-01-16 Toyota Central R&D Labs Inc ガス吸着材
EP2897929A4 (en) 2012-09-19 2016-06-01 Basf Se ACETYLENE BRIDGING BOND SEQUENCES AND METALLO-ORGANIC STRUCTURES (MOF) PRODUCED THEREFROM
CN103956502B (zh) * 2014-05-16 2016-03-30 复旦大学 一种基于金属有机骨架材料的锂-氧电池电极及其制备方法
CN105709692A (zh) * 2014-12-05 2016-06-29 中国石油化工股份有限公司 一种铜基金属有机骨架材料及其制备方法
JP6578704B2 (ja) 2015-03-31 2019-09-25 東ソー株式会社 多孔性配位高分子
CN108290134A (zh) 2015-11-27 2018-07-17 巴斯夫欧洲公司 金属-有机骨架的超快高空时产率合成
CN105642311A (zh) * 2015-12-29 2016-06-08 华南理工大学 碳基非贵金属贵金属核壳纳米催化剂及其以MOFs为模板的制备方法
WO2017210874A1 (en) * 2016-06-08 2017-12-14 Xia, Ling Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation
CN106477551A (zh) * 2016-10-13 2017-03-08 南京航空航天大学 一种金属有机框架衍生富氮多孔碳材料及其制备方法
CN108067278A (zh) * 2016-11-18 2018-05-25 中国科学院大连化学物理研究所 一种非贵金属多孔氮掺杂碳电催化剂的制备方法
CN108114697B (zh) 2016-11-29 2019-11-15 中国石油化工股份有限公司 一种磁性金属有机骨架材料及其制备方法
CN108114748B (zh) 2016-11-29 2020-03-17 中国石油化工股份有限公司 一种磁性杂多酸催化剂及其制备方法
CN106861634B (zh) * 2017-03-14 2020-03-31 潍坊学院 金属-有机骨架化合物@介孔材料复合材料及其制备方法与应用
JP7377106B2 (ja) 2017-08-22 2023-11-09 積水化学工業株式会社 組成物、成形体の製造方法及び成形体
CN108126727A (zh) * 2017-12-19 2018-06-08 广东省石油与精细化工研究院 一种室温降解甲醛催化剂及其制备方法和应用
CN108329484B (zh) * 2018-03-01 2020-05-22 华南理工大学 一种优先吸附乙烷的铁基双配体金属有机骨架材料及其制备方法与应用
CN108579815B (zh) * 2018-05-21 2020-10-09 安徽大学 一种双金属有机框架结构催化剂及其制备方法和应用
CN109232901B (zh) * 2018-07-24 2021-01-08 中国科学院合肥物质科学研究院 一种双金属有机骨架材料Fe/Mg-MIL-88B的制备方法和应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160211545A1 (en) * 2012-08-10 2016-07-21 The Regents Of The University Of California Solid lithium electrolyte via addition of lithium salts to metal-organic frameworks
CN103992339A (zh) * 2014-05-21 2014-08-20 哈尔滨工业大学 合成金属有机框架物材料Mg-MOF-74的方法
CN107949941A (zh) * 2015-09-08 2018-04-20 庄信万丰燃料电池有限公司 氧气还原反应催化剂
US20180226682A1 (en) * 2017-02-07 2018-08-09 University Of California, Los Angeles Composite electrolyte membrane, fabrication methods and applications of same
CN107759801A (zh) * 2017-09-27 2018-03-06 华南理工大学 利用晶体缺陷法合成中微双孔mof‑74材料的方法
CN109316978A (zh) * 2018-10-25 2019-02-12 上海科技大学 一种MOFs材料及其制备方法和用途
CN109638304A (zh) * 2018-12-29 2019-04-16 江苏大学 一种m-mof-74/石墨烯复合阴极材料的制备方法和用途

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113172234A (zh) * 2021-04-13 2021-07-27 南开大学 一种碳基单原子电催化剂的制备方法
CN113262810A (zh) * 2021-06-09 2021-08-17 四川大学 一种单原子催化剂m-sac及其制备方法和用途
CN114425365A (zh) * 2022-01-29 2022-05-03 重庆交通大学 富缺陷Mn-Co金属氧化物催化剂的制备方法
CN114425365B (zh) * 2022-01-29 2024-04-26 重庆交通大学 富缺陷Mn-Co金属氧化物催化剂的制备方法

Also Published As

Publication number Publication date
CN111769294B (zh) 2021-11-23
JP7253074B2 (ja) 2023-04-05
JP2022528911A (ja) 2022-06-16
CN111769294A (zh) 2020-10-13

Similar Documents

Publication Publication Date Title
WO2020199368A1 (zh) Mof化合物和非贵金属催化剂的制备方法
CN109103468B (zh) 一种铁、氮共掺杂炭氧还原催化剂及其制备方法和应用
Huang et al. Efficient oxygen reduction catalysts of porous carbon nanostructures decorated with transition metal species
Lu et al. Single‐atom catalytic materials for advanced battery systems
Tian et al. Metal-organic-framework-derived formation of Co–N-doped carbon materials for efficient oxygen reduction reaction
US11396521B2 (en) Ultra-thin Ni—Fe-MOF nanosheet, preparation method and use thereof
Liu et al. Structurally ordered Fe3Pt nanoparticles on robust nitride support as a high performance catalyst for the oxygen reduction reaction
Guan et al. Formation of single‐holed cobalt/N‐doped carbon hollow particles with enhanced electrocatalytic activity toward oxygen reduction reaction in alkaline media
Lv et al. Spin‐State Manipulation of Two‐Dimensional Metal–Organic Framework with Enhanced Metal–Oxygen Covalency for Lithium‐Oxygen Batteries
KR102572541B1 (ko) 산소 환원 반응 촉매
CN102728384B (zh) 铂-合金纳米粒子的合成和包含其的负载型催化剂
Huang et al. Direct immobilization of an atomically dispersed Pt catalyst by suppressing heterogeneous nucleation at− 40° C
Bai et al. Rational Design of Dodecahedral MnCo2O4. 5 Hollowed‐Out Nanocages as Efficient Bifunctional Electrocatalysts for Oxygen Reduction and Evolution
Xie et al. In situ growth of cobalt@ cobalt-borate core–shell nanosheets as highly-efficient electrocatalysts for oxygen evolution reaction in alkaline/neutral medium
Song et al. MOFs fertilized transition-metallic single-atom electrocatalysts for highly-efficient oxygen reduction: Spreading the synthesis strategies and advanced identification
CN105895886A (zh) 一种钠离子电池过渡金属磷化物/多孔碳负极复合材料及其制备方法
Guo et al. Hierarchical confinement of PtZn alloy nanoparticles and single-dispersed Zn atoms on COF@ MOF-derived carbon towards efficient oxygen reduction reaction
Wang et al. Hollow mesoporous carbon nanocages with Fe isolated single atomic site derived from a MOF/polymer for highly efficient electrocatalytic oxygen reduction
Miao et al. Synthesis and application of single-atom catalysts in sulfur cathode for high-performance lithium–sulfur batteries
Jiang et al. Phosphate Ion‐Functionalized CoS with Hexagonal Bipyramid Structures from a Metal–Organic Framework: Bifunctionality towards Supercapacitors and Oxygen Evolution Reaction
US11728492B2 (en) Atomically dispersed precursor for preparing a non-platinum group metal electrocatalyst
Li et al. In situ synthesis of oxidized MXene-based metal cobalt spinel nanocomposites for an excellent promotion in thermal decomposition of ammonium perchlorate
Zhang et al. Fe3C Decorated N, Fe Co‐Doped Hollow Carbon Microspheres as Efficient Air Electrode Catalyst for Zinc‐Air Battery
Wei et al. Three-phase composites of NiFe2O4/Ni@ C nanoparticles derived from metal-organic frameworks as electrocatalysts for the oxygen evolution reaction
Tuo et al. Constructing RuCoOx/NC Nanosheets with Low Crystallinity within ZIF‐9 as Bifunctional Catalysts for Highly Efficient Overall Water Splitting

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19922838

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021559482

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19922838

Country of ref document: EP

Kind code of ref document: A1