WO2019109212A1 - Matériau carboné métal-azote avec un métal dispersé à l'échelle atomique, son procédé de préparation et son utilisation - Google Patents

Matériau carboné métal-azote avec un métal dispersé à l'échelle atomique, son procédé de préparation et son utilisation Download PDF

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WO2019109212A1
WO2019109212A1 PCT/CN2017/114469 CN2017114469W WO2019109212A1 WO 2019109212 A1 WO2019109212 A1 WO 2019109212A1 CN 2017114469 W CN2017114469 W CN 2017114469W WO 2019109212 A1 WO2019109212 A1 WO 2019109212A1
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metal
carbon material
nitrogen
formamide
precursor
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PCT/CN2017/114469
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English (en)
Chinese (zh)
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孙晓明
张国新
贾茵
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北京化工大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment

Definitions

  • the invention belongs to the field of novel material preparation, in particular to a metal-nitrogen carbon material in which a metal is atomically dispersed, a preparation method thereof and use thereof.
  • Atomic-scale dispersed metal nitrogen-carbon composites are used in many important electrochemical reactions such as oxygen reduction and oxygen evolution due to their excellent catalytic performance, high utilization of metal components, high anti-pollution and high failure. Reaction, hydrogen evolution reaction, carbon dioxide reduction reaction.
  • the second is that the metal organic skeleton carbon material (MOF) can be used to uniformly chelate the characteristics of the transition metal component, and the MOF having a special element combination and content can be obtained to some extent to obtain a nitrogen-carbon material with atomic-level dispersion of the metal component.
  • MOF metal organic skeleton carbon material
  • the use of bimetallic ZnCo-MOF, subjected to high temperature roasting, can utilize the effect of Zn on the surrounding Co at high temperatures, greatly reducing the migration of the catalytic component Co, and producing a composite material of monoatomic Co-NC.
  • the composite exhibits excellent catalysis in the oxygen reduction reaction and has the same performance as the noble metal Pt carbon catalyst output.
  • the first preparation method obtains atomic-level dispersed metal nitrogen-carbon composites with extremely low efficiency, which relies heavily on pre-treatment and requires strict post-treatment to ensure that particulate metal components are removed and atomic grade metals.
  • the retention of the components, and the acid elution rate is greater than 50%, the content of the atomically dispersed metal component remaining in the metal-nitrogen carbon material is extremely low, usually not more than 1% by weight.
  • the efficiency of preparing the atomic grade metal nitrogen carbon material by the second material is much higher than that of the first preparation method, and the content of the atomic grade dispersed metal component remaining in the metal-nitrogen carbon material can be increased to 1.4 wt% to 5 wt%. It is very difficult to increase it, but it is also difficult to use it for a wide range of industrial production because of its expensive and toxic nature.
  • a first aspect of the invention provides a metal-nitrocarburethane precursor having a metal atomically dispersed, wherein the N content is 25-35 wt% and the metal content is 0.1- based on the total weight of the metal-nitrocarburethane precursor. 1.3 wt%, wherein the metal is one or more of a transition metal or a noble metal.
  • a second aspect of the present invention provides a method for preparing a metal-nitrogen carbon material precursor in which the above metal is atomically dispersed, comprising the steps of:
  • the metal salt solution of the metal salt is reacted at 120-300 ° C for 0.5 to 49 hours, so that the formamide therein is self-polymerized, and the solid-liquid separation is carried out after the reaction to obtain a metal-nitrogen-carbon material precursor in which the metal is atomically dispersed. body.
  • a third aspect of the present invention provides a metal-nitrogen carbon material in which a metal is atomically dispersed, wherein an N content is 4 to 7 wt% and a metal content is 0.3 to 8 wt% based on the total weight of the metal-nitrogen carbon material;
  • the metal is one or more of a transition metal or a noble metal.
  • the metal-nitrogen-carbon material in which the metal is atomically dispersed has a metal content of 5 to 8 wt%, more preferably a metal content of 6 to 8 wt%,
  • the metal-nitrocarburethane material composite has substantially the balance of carbon in addition to the metal element and the nitrogen element. "Basically” means that more than 99% of the balance is carbon, but there may be some impurities that are inevitably brought in during the preparation process.
  • the metal is one or more of a transition metal or a noble metal such as zinc, cobalt, iron, nickel, copper, manganese, chromium, tungsten, molybdenum, vanadium, niobium, tantalum or the like.
  • a transition metal or a noble metal such as zinc, cobalt, iron, nickel, copper, manganese, chromium, tungsten, molybdenum, vanadium, niobium, tantalum or the like.
  • the nitrogen-carbon material is a product obtained by calcining a formamide self-polymer under an inert atmosphere at 500 to 1000 °C.
  • the pickling means that the metal-nitrogen carbon material composite is immersed for a sufficient time with a non-oxidizing strong acid such as dilute sulfuric acid, hydrochloric acid, hydrofluoric acid or the like which can dissolve the metal or an oxide of the metal.
  • a non-oxidizing strong acid such as dilute sulfuric acid, hydrochloric acid, hydrofluoric acid or the like which can dissolve the metal or an oxide of the metal.
  • Pickling is an effective method for testing free metals and metal oxides. If free metals or metal oxides are present, they are dissolved by these non-oxidizing strong acids. The ratio of the amount of dissolved metal to the total amount of metal is defined as metal. Elution rate.
  • the metal pickling elution rate is less than 6.4%, indicating that most of the metals are not present in the free elemental state and the oxide form, but are combined with the nitrogen-carbon material by chemical bonds.
  • a fourth aspect of the invention provides the method for preparing a metal-nitrogen carbon material according to the third aspect, comprising the steps of:
  • a metal salt is dissolved in formamide to prepare a solution of a metal salt in formamide, wherein the metal is one or more of a transition metal or a noble metal;
  • the metal salt solution of the metal salt is reacted at 120-300 ° C for 0.5 to 49 hours, so that the formamide therein is self-polymerized, and the solid-liquid separation is carried out after the reaction to obtain a metal-nitrogen-carbon material precursor in which the metal is atomically dispersed. body;
  • the foregoing precursor is calcined at 500-1000 ° C for 0.5 to 30 hours under an inert atmosphere to obtain the metal-nitrogen carbon material.
  • the concentration of the metal salt in the formamide solution is not higher than the saturated solubility of the metal salt in the formamide.
  • the formamide solution of the metal salt is subjected to effective mixing after dissolution. Effective mixing means include but not limited For manual oscillation, mechanical oscillation, ultrasonic, stirring, etc. More preferably, in step A, some zinc salt may be further dissolved in the formamide solution of the target metal salt to increase the content of the target metal component in the final metal-nitrocarbon material composite.
  • the formamide will self-polymerize to form a nitrogen-doped carbon material, and at the same time, the nitrogen element on the formamide will preferentially chelate the metal cation, so that the metal ions are distributed in the atomic-level dispersed state. Miscellaneous carbon material.
  • the process of self-polymerization of metalformamide and metal ion bonding with its self-polymer is complicated. It is presumed that the process may be as follows: the molecular formula of formamide is HCONH2, which has only four elements of carbon, nitrogen, hydrogen and oxygen, and dehydration occurs during self-polymerization.
  • step B removing most of the hydrogen and oxygen elements to obtain a nitrogen-doped carbon material, wherein the nitrogen content is about 25-35 wt%, and wherein the metal ions are dispersed at the atomic level and doped with the chemical bond with the nitrogen Bonding of carbon materials.
  • the product can be optionally separated from the reaction liquid by an effective means, and the solid product is dried.
  • step C after calcination under an inert atmosphere, the product of the step B removes all of the hydrogen element and a part of the nitrogen element, leaving only nitrogen, carbon and metal elements, and the metal of the third aspect of the invention is obtained. Nitrogen carbon material.
  • a zinc salt is added in the step A, it is necessary to make the calcination temperature in the step C higher than 700 ° C, more preferably higher than the boiling point of 908 ° C in the zinc.
  • the metal in the present invention is atomically dispersed and chemically bonded to the nitrogen carbon material
  • the metal-nitrogen carbon material which is embodied in the third aspect of the invention is characterized in that the nitrogen content is extremely high and can reach 4- 7wt%, and the metal is atomically dispersed and the content is extremely high, and can reach 0.3-8wt%; preferably, the metal content is 5-8wt%, more preferably 6-8wt%, and the metal pickling elution rate is lower than 6.4. %.
  • a fifth aspect of the invention relates to the use of the metal-nitrocarburethane precursor or metal-nitrogen carbon material as an electrochemical reaction catalyst.
  • the electrochemical reaction comprises an oxygen reduction reaction, an oxygen evolution reaction, a hydrogen evolution reaction or a carbon dioxide reduction reaction.
  • the invention may also have other uses that are yet to be developed.
  • the metal-nitrogen carbon precursor obtained by the present invention has a nitrogen content of 25 to 35 wt%, and such a high nitrogen content is difficult to achieve by doping nitrogen into the carbon material by other methods, and further, since the metal cation is Chelating with nitrogen, the high content of nitrogen ensures that more metals can be chelated, laying the foundation for subsequent metal content enhancement.
  • the metal-nitrogen carbon material obtained by calcining the metal-nitrogen carbon material precursor at a high temperature will have a much higher metal content than other methods for preparing a metal nitrogen-carbon composite (for example, the method described in the background section). The metal content that can be achieved.
  • the metal-nitrogen carbon material obtained by the invention has strong stability.
  • the nitrogen-carbon material itself is highly stable since it has undergone the high-temperature calcination process of step C.
  • the metal is chemically bonded to the nitrogen-carbon material, the metal is also highly stable, as shown by its elution rate after pickling is less than 6.4%.
  • the metal is in an atomic-scale dispersed state. Considering that the metal component is a core functional component of many catalysts, and generally the higher the metal content, the better the metal dispersion, the better the catalytic effect. Therefore, the metal component having such a high loading amount, which is atomically dispersed and highly stable, has laid the invention.
  • the metal-nitrogen carbon material precursor of the present invention can also be used as an electrochemical reaction catalyst, but since the precursor can be dissolved by a high concentration of strong acid and strong alkali, it can only be applied to an electrolyte without using a high concentration of strong acid. The occasion of strong alkali.
  • the preparation method of the invention has the advantages of low cost, low toxicity, simple and easy reaction operation, and suitable for industrial expansion, and the atomic-level dispersed metal nitrogen carbon material has high preparation efficiency, and the preparation method is not limited to the type and valence of the metal.
  • the preparation strategy of the present invention is also highly feasible for the preparation of a combined nitrogen-carbon material of a multi-metal component, and can be used to study the synergistic effect of a multi-atomic dispersed metal component on electrochemical catalysis.
  • step D by adding a soluble zinc salt in the step A and calcining at a temperature higher than 700 ° C in the step C, the metal content of the finished product obtained by adding no soluble zinc salt under the same conditions is more. High and can achieve a higher dispersion of the remaining metals.
  • This phenomenon is surprising, and there is no particularly reasonable explanation for this applicant. It is speculated that it may be because during the reaction of step B, zinc promotes more chelation of metal with N atoms, and zinc and other metals After sequestration to the N atoms at intervals, and then evaporating off the zinc at a high temperature, the dispersion of the remaining metals is improved.
  • TEM 1 is a transmission electron microscope (TEM) characterization image of a metal-nitrogen carbon precursor prepared in Examples 1-14 of the present invention, and no metal element or metal oxide particles were observed.
  • STEM 2 is a dark field scanning transmission electron microscope (STEM) characterization image of a metal-nitrogen carbon precursor prepared in Examples 1-14 of the present invention, and the metal is monoatomic dispersed and dispersed in density. Higher.
  • XRD X-ray diffraction
  • TEM 4 is a transmission electron microscope (TEM) characterization image of a metal-nitrogen carbon material according to Examples 15-17 of the present invention.
  • Embodiment 15-17 is a dark field scanning transmission electron microscope (STEM) characterization image of the metal-nitrogen carbon material according to Embodiment 15-17 of the present invention. It can be seen from the image that the metal is in a monoatomic state and the dispersion density is high. .
  • STEM dark field scanning transmission electron microscope
  • Fig. 6 is an X-ray diffraction (XRD) pattern of the metal-nitrogen carbon material according to Example 15-17 of the present invention, and the spectrum shows a metal-free element, a metal oxide or the like.
  • XRD X-ray diffraction
  • Figure 7 is a transmission electron microscope (TEM) characterization image of the metal-nitrogen carbon material prepared in Examples 1A-14A of the present invention, and no metal element or metal oxide particles were observed.
  • TEM transmission electron microscope
  • Example 8 is a dark field scanning transmission electron microscope (STEM) characterization image of the metal-nitrogen carbon material prepared in Example 1A-14A of the present invention. It can be seen from the image that the metal is in a monoatomic state with a high dispersion density. .
  • STEM dark field scanning transmission electron microscope
  • Figure 9 is an X-ray diffraction (XRD) pattern of the metal-nitrogen carbon material prepared in Example 1A-14A of the present invention, and the spectrum shows no significant metal element, metal oxide or the like.
  • XRD X-ray diffraction
  • a certain amount of metal salt was dissolved in 30 mL of formamide, ultrasonically dispersed to be transparent, and then placed in a volume of 40.0 mL of a Teflon reactor at the reaction temperature shown in Table 1. React with time. After the reaction is completed, the temperature is naturally lowered, the solid-liquid mixture is taken out, the solid-liquid separation is carried out by centrifugation, and the solid is dried in an oven at 60 ° C to collect a dry powder, which is a metal-nitrogen carbon material precursor in which the metal is atomically dispersed.
  • the precursors shown in Examples 1-14 were subjected to measurement of nitrogen content and metal content and pickling elution rate, wherein the metal elution rate was determined after soaking the target product with 1 mol/L of dilute sulfuric acid for 2 hours. Shown in Table 1.
  • each precursor was calcined under the argon atmosphere at the calcination temperature and time shown in Table 1, to obtain a target product, that is, a metal-nitrogen carbon material in which the metal was atomically dispersed, which were numbered as Examples 1A-14A and implemented.
  • a target product that is, a metal-nitrogen carbon material in which the metal was atomically dispersed, which were numbered as Examples 1A-14A and implemented.
  • Example 15-17 Elemental analysis of the target product revealed that it consisted essentially of only nitrogen, carbon and metals. The data of the nitrogen content, the metal content, and the metal elution rate after pickling of the target product are also listed in Table 1.
  • Example 15 is compared with Example 1A, Example 16 and Example 11A, and Example 17 and Example 12A, and it is also apparent that when a zinc salt is additionally added to the metal salt solution of the metal salt and in the step C, Calcination above 700 °C can significantly increase the metal content in the final product after calcination, and the metal acid elution rate of the calcined product is also lower than that in the absence of zinc salt, indicating that the zinc salt promotes more The metal is directly complexed with N and the metal is more dispersed.
  • Examples 1-14 and Examples 1A-14A and Examples 15-17 were used for electrocatalytic oxygen reduction (ORR), oxygen evolution (OER) and hydrogen evolution (HER), respectively.
  • ORR electrocatalytic oxygen reduction
  • OER oxygen evolution
  • HER hydrogen evolution
  • the initial potential and the half-wave potential were compared with a commercial Pt/C catalyst (platinum content of 20% by weight) and Ir/C catalyst (Ir content of 20% by weight), and the results are shown in Table 2 below.
  • Oxygen reduction test conditions test linear sweep voltammetry curve in 0.1mol/L KOH solution, oxygen saturation, 1600rpm, sweep speed 5mV/s; oxygen precipitation test conditions: in 0.1mol/L KOH solution, The linear sweep voltammetry curve was tested at a speed of 1600 rpm and a sweep rate of 5 mV/s.
  • the hydrogen evolution reaction test conditions were tested in a 0.5 mol/L H 2 SO 4 solution at a rotational speed of 1600 rpm and a sweep rate of 5 mV/s. An curve.
  • the metal in the present invention is a metal-nitrogen carbon precursor which is atomically dispersed, and has a certain catalytic effect on the electrocatalytic oxygen reduction reaction, the oxygen evolution reaction and the hydrogen evolution reaction, but the metal after calcination
  • a metal-nitrogen-carbon material dispersed in an atomic order which has a better catalytic effect, which is reflected in the fact that in their oxygen reduction reaction and hydrogen evolution reaction, the initial reaction potential is higher, the half-wave potential is higher, and oxygen is precipitated.
  • the initial potential and half-wave potential are lower in the reaction, and its catalytic effect is equivalent to or even superior to current commercial Pt/C catalysts and commercial Ir/C catalysts.
  • the present invention utilizes a less expensive transition metal as an active component and has a higher metal utilization efficiency, and thus is more cost effective than a commercial Pt/C catalyst and a commercial Ir/C catalyst.
  • the metal component may also be ruthenium chloride, tin chloride, palladium chloride or the like, which will not be enumerated here. Rather, the above-described embodiments are merely illustrative of the invention, and are not intended to limit the scope of the embodiments.

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Abstract

L'invention concerne un précurseur de matériau carboné métal-azote avec le métal dispersé à l'échelle atomique, la teneur en N étant de 25 à 35 % en poids et la teneur en métal étant de 0,1 à 1,3 % en poids, sur la base du poids total du précurseur de matériau carboné métal-azote, le métal étant un ou plusieurs métaux de transition ou métaux nobles. Le précurseur est formé par auto-polymérisation d'une solution formamide d'un sel métallique. Le matériau carboné métal-azote avec le métal dispersé à l'échelle atomique est obtenu par grillage à haute température du précurseur dans une atmosphère inerte, la teneur en N étant de 4 à 7 % en poids et la teneur en métal étant de 0,3 à 8 % en poids, sur la base du poids total du matériau carboné métal-azote. Le précurseur et le matériau carboné métal-azote peuvent tous les deux être utilisés en tant que catalyseur électrochimique. Le procédé de préparation est simple, facile à utiliser et économique, et possède un rendement de préparation élevé pour le matériau carboné métal-azote avec une dispersion à l'échelle atomique.
PCT/CN2017/114469 2017-12-04 2017-12-04 Matériau carboné métal-azote avec un métal dispersé à l'échelle atomique, son procédé de préparation et son utilisation WO2019109212A1 (fr)

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CN113373474A (zh) * 2021-06-08 2021-09-10 北京化工大学 一种金属原子级分散氮碳材料的溶剂循环制备方法及用途

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CN113373474A (zh) * 2021-06-08 2021-09-10 北京化工大学 一种金属原子级分散氮碳材料的溶剂循环制备方法及用途

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