WO2021051896A1 - 一种掺氮碳包裹四氧化三钴纳米线整体式催化剂及其制备方法 - Google Patents

一种掺氮碳包裹四氧化三钴纳米线整体式催化剂及其制备方法 Download PDF

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WO2021051896A1
WO2021051896A1 PCT/CN2020/095322 CN2020095322W WO2021051896A1 WO 2021051896 A1 WO2021051896 A1 WO 2021051896A1 CN 2020095322 W CN2020095322 W CN 2020095322W WO 2021051896 A1 WO2021051896 A1 WO 2021051896A1
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nitrogen
monolithic catalyst
carbon
catalyst according
cobalt
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PCT/CN2020/095322
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English (en)
French (fr)
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谌春林
周振强
张建
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中国科学院宁波材料技术与工程研究所
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Publication of WO2021051896A1 publication Critical patent/WO2021051896A1/zh

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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B01J35/398—

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  • the application relates to a nitrogen-doped carbon-coated cobalt tetroxide nanowire monolithic catalyst and a preparation method thereof.
  • Cobalt is a common transition metal. Compared with precious metals such as gold, platinum, ruthenium and iridium, cobalt has more abundant reserves, lower price, and certain catalytic performance, so it has become a popular material in the field of catalysis. However, the catalytic efficiency of pure metal cobalt is low, and its catalytic performance is downstream in the known materials, while its high oxidation state Co3O4 shows excellent catalytic activity in many catalytic reactions.
  • cobalt tetroxide catalysts are mostly in powder or nano-particle structure. Direct use as a catalyst faces many problems such as difficulty in dispersion and separation, uneven mass transfer and contact in the catalytic reaction process; adding a binder to form a bulk material will increase the cost and reduce the catalytic activity . Therefore, the direct growth of active structure of cobalt tetroxide with controllable composition and morphology on the catalyst support has important theoretical and practical significance.
  • this application provides a nitrogen-doped carbon-coated cobalt tetroxide nanowire monolithic catalyst and a preparation method thereof.
  • the active material cobalt tetroxide is directly grown on the carrier, and the morphology of the active material is controllable, which improves the catalytic activity of the catalyst. And stability.
  • a monolithic catalyst is provided.
  • the monolithic catalyst includes a carrier and an active material carried on the carrier;
  • the active material includes nitrogen-doped carbon nanowires encapsulating cobalt tetroxide particles.
  • the active substance grows in situ on the surface of the carrier.
  • the morphology of the active material is a dendritic shape formed by nitrogen-doped carbon nanowires encapsulating cobalt tetroxide particles.
  • the carrier is selected from at least one of foamed metal, foamed carbon, and carbon fiber cloth;
  • the particle size of cobalt tetroxide particles is 3-10nm;
  • the diameter of the nanowire is 40-60nm
  • the length of the nanowire is 500 ⁇ 2000nm
  • the molar content of nitrogen in the active material is 0.5% to 2%; the molar content of carbon in the active material is 20% to 40%; the molar content of cobalt in the active material is 5% to 10%.
  • the upper limit of the molar content of the nitrogen element in the active material is selected from 1%, 1.5% or 2%; the lower limit is selected from 0.5%, 1% or 1.5%.
  • the upper limit of the molar content of the cobalt element in the active material is selected from 6%, 7%, 8%, 9% or 10%; the lower limit is selected from 5%, 6%, 7%, 8% or 9%.
  • Another aspect of the present application provides a method for preparing a monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst that is simple to prepare, low in cost, strong in catalytic performance, long in service life, and extremely easy to separate.
  • the preparation method of the monolithic catalyst includes the following steps:
  • the molar ratio of the cobalt element in the cobalt source, the nitrogen element in the nitrogen source, and the carbon element in the carbon source to water in the aqueous solution in step S100 is 1:3-10:1.5-50:600-1200.
  • the cobalt source is selected from CoF 2, CoCl 2, CoBr 2 , CoI 2, CoCO 3, Co (NO 3) 2, CoSO 4, at least one of;
  • the nitrogen source is selected from at least one of urea and tetrasodium edetate;
  • the carbon source is selected from at least one of urea and tetrasodium edetate.
  • the temperature of the heating reaction in step S200 is 110° C. to 160° C., and the time of the heating reaction is 8 to 24 h;
  • Step S200 is: immersing the carrier in an aqueous solution, heating and reacting, washing, and drying to obtain a precursor;
  • Washing is: rinse with water and ethanol for 2 to 3 times in sequence;
  • the drying conditions are: drying at 60°C ⁇ 80°C for 8h ⁇ 12h.
  • the protective gas in step S300 is selected from at least one of nitrogen, argon, and helium;
  • the flow rate of the shielding gas is 100mL/min ⁇ 180mL/min.
  • the temperature of the heating reaction in step S300 is 300° C. to 400° C.
  • the time of the heating reaction is 0.5 h to 1 h.
  • the conditions for the heating reaction in step S300 are: heating from room temperature to 300°C to 400°C at a rate of 4°C/min to 8°C/min, and after holding for 0.5h to 1h, heating at a rate of 2°C/min to 3°C Cool to room temperature at a rate of /min.
  • the monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst has a macroscopic morphology and hierarchical structure, which can provide strength and effective mass transfer channels for reactants suitable for practical applications.
  • the carbon-coated design can It blocks the corrosion of exposed metals by acids and bases, prolongs the service life of the catalyst, and at the same time builds a confined space. Nitrogen doping can increase the local electron cloud density on the carbon surface and improve the catalytic performance. Compared with cobalt-based powder catalyst, it is easier to separate after use.
  • the method for preparing the monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst provided by this application has high catalytic efficiency, strong catalytic stability, long service life, and easy separation from the product after use.
  • Figure 1 is an XRD spectrum of the monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst and its surface exfoliated components prepared in Example 1 of the application;
  • Figure 2 is a scanning electron microscope image of the monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst prepared in Example 1 of the application; where (a) is the scale bar is 5 ⁇ m, (b) is the scale bar is 500 ⁇ m, and (c) is The scale bar is 50 ⁇ m;
  • Figure 3 is a transmission electron microscope image of the exfoliated material on the surface of the monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst prepared in Example 1 of the application; where (a) is the scale bar is 0.2 ⁇ m, (b) is the scale bar is 100 nm, (c) The scale bar is 5nm;
  • Example 4 is an X-ray electron spectrogram of the monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst prepared in Example 1 of the application;
  • Example 5 is a STEM element distribution diagram of the monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst prepared in Example 1 of the application; where (a) is carbon element, (b) is nitrogen element, and (c) is oxygen Element, (d) is cobalt element.
  • the Bruker D8 DISCOVER X-ray diffractometer was used for XRD analysis with Cu as the target.
  • the FEI F20 transmission electron microscope was used for TEM analysis at 200kV.
  • the Kratos AXIS ULTRA DLD equipment was used to perform X-ray electron spectroscopy analysis with Al as the target.
  • the monolithic catalyst includes a carrier and an active material carried on the carrier;
  • the active material includes nitrogen-doped carbon nanowires encapsulating cobalt tetroxide particles.
  • the preparation method of the monolithic catalyst includes the following steps:
  • the nitrogen-containing and carbon-containing compound is one or two of urea and tetrasodium edetate.
  • the concentration of the prepared solution there is no particular limitation on the concentration of the prepared solution.
  • the molar ratio of Co(NO 3 ) 2 to water is 1:600-1: 1200.
  • hydrothermal reaction put the solution obtained in step S100 in a reaction kettle, add a carrier such as foamed metal or foamed carbon or carbon fiber cloth, and keep it at 110°C ⁇ 160°C for 8h ⁇ 24h, wash and dry to obtain the precursor .
  • a carrier such as foamed metal or foamed carbon or carbon fiber cloth
  • step S200 there are no special restrictions on the added carrier such as metal foam, carbon foam, or carbon fiber cloth.
  • the specifications of the carrier such as foamed metal or foamed carbon or carbon fiber cloth are sufficient to be immersed in the solution.
  • the precursor is obtained through a hydrothermal reaction, wherein the hydrothermal temperature is 110° C. to 160° C., and the heating time is 8 h to 24 h.
  • the surface of the precursor obtained by the reaction is covered with a small amount of precipitate.
  • a washing operation is required.
  • the washing method is: washing the precursor with water and ethanol successively for 2 to 3 times.
  • the drying conditions are: drying at 60°C to 80°C for 8 hours to 12 hours.
  • step S300 carbonization process: place the precursor obtained in step S200 in a heating furnace, pass in protective gas, and keep it at 300°C ⁇ 400°C for 0.5h ⁇ 1h. After cooling, a monolithic nitrogen-doped carbon-coated cobalt tetroxide can be obtained Nanowire catalyst.
  • the target monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst is obtained through the carbonization process.
  • the heating furnace is preferably a tube furnace with a built-in quartz tube or corundum tube, and the protective gas is preferably nitrogen, One or more of argon and helium.
  • the flow rate of the shielding gas should not be too large, and the flow rate is preferably 100 mL/min to 180 mL/min. At this flow rate, the ablation of the product can be prevented, and the purity of the product can be ensured, thereby improving the physical and chemical properties of the product.
  • step S300 the heating method adopts a one-step heating method.
  • the heating speed should not be too fast.
  • the temperature control process of the heating furnace is: heating from room temperature to 8°C/min at a rate of 4°C/min to 8°C/min 300°C ⁇ 400°C, after holding for 0.5h ⁇ 1h, cooling to room temperature at a rate of 2°C/min ⁇ 3°C/min.
  • the role of nitrogen and carbon compounds is to provide both a source of N and a source of C, forming a nitrogen-doped carbon coating layer, reducing the corrosion of cobalt by acid and alkali, and prolonging the service life of the catalyst.
  • the loading amount of Co element and the doping concentration of N atoms can be adjusted by the initial ratio of each raw material.
  • the preparation of the monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst of the present invention adopts a simple operation method, has low equipment and technical requirements, uses common chemical raw materials, and has low cost; in the catalyst obtained by the method of the present invention, N The atoms are evenly distributed,
  • the loading amount of Co element and the doping concentration of N atoms are adjustable, so as to meet the application under different conditions; and the monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst obtained by the present invention has a higher content of doped carbon with good conductivity , And the cobalt tetroxide nanowires work together to make the catalyst have high conductivity and longer service life; in addition, the monolithic catalyst prepared by this method has more mass transfer pores than the nanopowder catalyst, and it is easier to interact with the catalytic product after use.
  • step (2) Transfer the solution prepared in step (1) to a 100mL reactor, add the foamed nickel carrier, so that it is immersed in the solution, put it in an oven and react at 120°C for 8h, take it out and rinse with water and ethanol twice in sequence , Placed in a beaker, placed in an oven and dried at 60°C for 12 hours to obtain a precursor.
  • step (3) Put the precursor obtained in step (2) in the quartz boat of the tube furnace, and pass high-purity nitrogen as the full protective gas after sealing.
  • the flow rate of nitrogen is 150 mL/min; after 30 minutes of ventilation, the temperature is 5°C/min.
  • the temperature was raised to 350°C at a rate of min. After holding for 0.5h, it was cooled to room temperature at a rate of 3°C/min.
  • the product obtained was a monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst grown on foamed nickel, which was recorded as sample 1 .
  • Example 1 Compared with Example 1, the quality of urea in the raw materials used in this example has changed, and the other preparation conditions are unchanged. As the quality of urea decreases, the nitrogen-doped carbon coating layer of the finally obtained catalyst becomes thinner. The amount of nitrogen doping is reduced.
  • step (2) Transfer the solution prepared in step (1) to a 100mL reaction kettle, add the foamed nickel carrier, so that it is immersed in the solution, put it in an oven and react at 140°C for 8 hours, take it out and rinse with water and ethanol twice in sequence , Placed in a beaker, placed in an oven and dried at 60°C for 12 hours to obtain a precursor.
  • Example 1 Compared with Example 1, the temperature of the hydrothermal reaction used in this example has changed, and the rest of the preparation conditions are unchanged. With the increase of the hydrothermal reaction temperature, the nitrogen-doped carbon-coated cobalt tetroxide nanowires finally obtained The diameter of the nanowires of the catalyst becomes larger.
  • step (2) Transfer the solution prepared in step (1) to a 100mL reaction kettle, add carbon fiber cloth, so that it is immersed in the solution, put it in an oven to react at 120°C for 12h, take it out, and rinse it with water and ethanol twice. Place it in a beaker and put it in an oven to dry at 60°C for 12 hours to obtain a precursor.
  • step (3) Put the precursor obtained in step (2) in the quartz boat of the tube furnace, and then pass in high-purity argon as the full protective gas after sealing, and the nitrogen flow rate is 120mL/min; after 40 minutes of ventilation, the temperature is 5°C The temperature was raised to 350°C at a rate of 1/min. After holding for 0.5h, it was cooled to room temperature at a rate of 2°C/min. The product obtained was a monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst grown on carbon fiber cloth, which was recorded as sample 4 .
  • step (2) Transfer the solution prepared in step (1) to a 100mL reaction kettle, add the foamed carbon carrier, so that it is immersed in the solution, put it in an oven and react at 130°C for 8 hours, take it out and rinse with water and ethanol twice in sequence , Placed in a beaker, placed in an oven and dried at 60°C for 12 hours to obtain a precursor.
  • step (3) Put the precursor obtained in step (2) in the quartz boat of the tube furnace, and then pass in high-purity argon as the full protective gas after sealing, the flow of nitrogen is 140mL/min; after 30 minutes of ventilation, the temperature is 5°C The temperature was raised to 400°C at a rate of 1/min, and after holding for 0.5h, it was cooled to room temperature at a rate of 3°C/min.
  • the product obtained was a monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst grown on foamed carbon, which was recorded as a sample 5.
  • FIG. 1 shows the XRD spectra of sample 1 and the nitrogen-doped carbon-coated cobalt tetroxide nanowire powder mechanically stripped from the nickel foam and the sample before stripping. It can be seen from the figure that the stripped powder sample is 31.27 at the 2-Theta angle.
  • Samples 2 to 3 and the nitrogen-doped carbon-coated cobalt tetroxide nanopowders mechanically peeled off from the foamed nickel were subjected to XRD tests.
  • the difference in peak intensity is only the same as that in Fig. 1, and the characteristic peaks are all consistent.
  • Sample 4 and the nitrogen-doped carbon-coated cobalt tetroxide nanopowder mechanically peeled from the carbon fiber cloth were subjected to XRD test.
  • the stripped nitrogen-doped carbon-coated cobalt tetraoxide nanopowder and the stripped nitrogen-doped carbon-coated cobalt tetraoxide nanopowder in Figure 1 were peeled off. Only the difference in peak intensity, the characteristic peaks are consistent.
  • Sample 5 and the nitrogen-doped carbon-coated cobalt tetroxide nanopowder mechanically peeled from the foamed carbon were subjected to XRD test.
  • the stripped nitrogen-doped carbon-coated cobalt tetraoxide nanopowder and the stripped nitrogen-doped carbon-coated cobalt tetroxide nanopowder in Figure 1 were peeled off. Only the difference in peak intensity, the characteristic peaks are consistent.
  • Samples 1 to 5 and the nitrogen-doped carbon mechanically stripped from the carrier were coated with cobalt tetroxide nanopowder for SEM and TEM testing.
  • 2 is a scanning electron microscope image of the monolithic nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst grown on the foamed nickel obtained in Example 1. It can be seen that the microstructure of the catalyst is pine branch-like.
  • Figure 3 is a transmission electron microscope image of the mechanically stripped nitrogen-doped carbon-coated cobalt tetroxide nanowire catalyst obtained in this example. It can be seen from the figure that the catalyst nanowire has a diameter of about 50 nm and a length greater than 500 nm.
  • the SEM images and TEM images of samples 4 to 5 and the nitrogen-doped carbon-coated cobalt tetroxide nanopowder mechanically peeled from the carrier are similar to sample 1, except for the difference between the carrier and the diameter of the nanowire.
  • Nitrogen-doped carbon which was mechanically peeled off the carrier from samples 1 to 5, was coated with cobalt tetraoxide nanopowder for X-ray electron spectroscopy.
  • Figure 4 is the X-ray electron spectrogram of sample 1 in Example 1. The results show that the percentages of the elements on the catalyst surface are C (37.65at%), N (1.08at%), Co (7.27at%) and The carrier nickel element, the total cobalt content determined by inductively coupled plasma mass spectrometer ICP is 20.1at%, so it is proved that the cobalt is actually wrapped by the nitrogen-doped carbon layer in the form of Co 3 O 4.
  • FIG. 1 is a STEM element distribution diagram of sample 1 in Example 1, showing that carbon, nitrogen, oxygen, and cobalt are uniformly distributed.

Abstract

本申请公开了一种整体式催化剂，所述整体式催化剂包括载体和负载于载体上的活性物质；所述活性物质包括包裹四氧化三钴颗粒的氮掺杂碳纳米线。本申请还公开了该整体式催化剂的制备方法。该整体式催化剂中四氧化三钴纳米线被氮掺杂的碳层包裹，产品质量好，导电性高，使用寿命长。

Description

一种掺氮碳包裹四氧化三钴纳米线整体式催化剂及其制备方法 技术领域
本申请涉及一种掺氮碳包裹四氧化三钴纳米线整体式催化剂及其制备方法。
背景技术
钴是一种常见的过渡金属，较之金、铂、钌和铱等贵金属，其储量更加丰富，价格更加低廉，同时具有一定的催化性能，因此成为催化领域的热门材料。然而，纯金属钴的催化效率较低，催化性能在已知材料中处于下游，而其高氧化态的四氧化三钴却在诸多催化反应中表现出优良的催化活性。研究表明，通过掺杂改性、包裹外壳或制成纳米材料调控四氧化三钴的表面缺陷、电荷分布、微观形貌，可以进一步提高四氧化三钴的催化效率，并增强其在催化反应中的稳定性，延长催化剂的使用寿命。
目前，四氧化三钴催化剂多为粉末状或纳米颗粒结构，直接作为催化剂使用面临分散和分离困难、催化反应过程传质接触不均等诸多问题；添加粘结剂形成块体材料又会增加成本、降低催化活性。因此，在催化剂载体上直接生长组分和形貌可控的四氧化三钴活性结构，具有重要的理论和实际意义。
发明内容
为了解决上述技术问题，本申请提供了一种掺氮碳包裹四氧化三钴纳米线整体式催化剂及其制备方法，活性物质四氧化三钴直接生长在载体上，且活性物质的形貌可控，提高了催化剂催化活性和稳定性。
为实现上述目的，本申请采用的技术方案如下：
本申请一方面，提供了一种整体式催化剂。
所述整体式催化剂包括载体和负载于载体上的活性物质；
活性物质包括包裹四氧化三钴颗粒的氮掺杂碳纳米线。
可选地，活性物质原位生长于所述载体表面。
可选地，活性物质的形貌为包裹四氧化三钴颗粒的氮掺杂碳纳米线形成的枝状。
可选地，载体选自泡沫金属、泡沫碳、碳纤维布中的至少一种；
四氧化三钴颗粒的粒径为3～10nm；
纳米线的直径为40～60nm；
纳米线的长度为500～2000nm；
活性物质中氮元素的摩尔含量为0.5％～2％；活性物质中碳元素的摩尔含量为20％～40％；活性物质中钴元素的摩尔含量为5％～10％。
可选地，活性物质中氮元素的摩尔含量的上限选自1％、1.5％或2％；下限选自0.5％、1％或1.5％。
可选地，活性物质中钴元素的摩尔含量的上限选自6％、7％、8％、9％或10％；下限选自5％、6％、7％、8％或9％。
本申请的另一方面，提供了一种制备简单、成本低廉、催化性能强、使用寿命长、极易分离的载体上原位生长的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂的制备方法。
所述整体式催化剂的制备方法，包括以下步骤：
S100：获得含有钴源、氮源、碳源的水溶液；
S200：将载体浸没于水溶液中，加热反应，得到前驱体；
S300：将前驱体在保护气体的气氛中，加热反应，得到整体式催化剂。
可选地，步骤S100中水溶液中钴源中的钴元素、氮源中的氮元素、碳源中的碳元素与水的摩尔比为1:3～10:1.5～50：600～1200。
可选地，钴源选自CoF 2、CoCl 2、CoBr 2、CoI 2、CoCO 3、Co(NO 3) 2、CoSO 4中的至少一种；
氮源选自尿素、乙二胺四乙酸四钠中的至少一种；
碳源选自尿素、乙二胺四乙酸四钠中的至少一种。
可选地，步骤S200中加热反应的温度为110℃～160℃，加热反应的时间为8～24h；
步骤S200为：将载体浸没于水溶液中，加热反应，洗涤，干燥，得到前驱体；
洗涤为：依次使用水和乙醇冲洗2～3次；
干燥条件为：60℃～80℃下干燥8h～12h。
可选地，步骤S300中保护气体选自氮气、氩气、氦气中的至少一种；
保护气体的流量为100mL/min～180mL/min。
可选地，步骤S300中加热反应的温度为300℃～400℃，加热反应的时间为0.5h～1h。
可选地，步骤S300中加热反应的条件为：以4℃/min～8℃/min的速度由室温升温至300℃～400℃，保温0.5h～1h后，以2℃/min～3℃/min的速度冷却至室温。
本申请的有益效果在于：
1)本申请所提供的整体式催化剂的制备方法，简单，原料易得，产量高，且对设备和技术要求低。
2)本申请所提供的整体式催化剂，整体式氮掺杂碳包裹四氧化三钴纳米线催化剂具有宏观形貌和分级结构，能够提供适合实际应用的强度和反应物有效传质通道，碳包覆设计能够阻隔酸碱对暴露金属的腐蚀，延长催化剂的使用寿命，同时构建限域空间，氮掺杂能够提升碳表面局域电子云密度，提升催化性能。与钴基粉末催化剂相比，使用后更易分离。
3)本申请所提供的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂的制备方法，通过该方法制备出的催化剂催化效率高，催化稳定性强，使用寿命长，在使用后容易与产物分离。
附图说明
图1为本申请实施例1中制得的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂及其表面剥落成分的XRD谱图；
图2为本申请实施例1中制得的整体式氮掺杂碳包裹四氧化三钴 纳米线催化剂的扫描电镜图；其中，(a)为比例尺为5μm，(b)为比例尺为500μm，(c)为比例尺为50μm；
图3为本申请实施例1中制得的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂表层剥落物的透射电镜图；其中，(a)为比例尺为0.2μm，(b)为比例尺为100nm，(c)为比例尺为5nm；
图4为本申请实施例1中制得的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂的X光电子能谱图；
图5为本申请实施例1中制得的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂的STEM元素分布图；其中，(a)为碳元素，(b)为氮元素，(c)为氧元素，(d)为钴元素。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
如无特别说明，本申请的实施例中的原料和催化剂均通过商业途径购买。
本申请的实施例中分析方法如下：
利用Bruker D8 DISCOVER X射线衍射仪以Cu为靶材进行XRD分析。
利用HITACHI S-4800扫描电子显微镜在8.0kV下进行SEM分析。
利用FEI F20透射电子显微镜在200kV下进行TEM分析。
利用Kratos AXIS ULTRA DLD设备以Al为靶材进行X光电子能谱分析。
利用SPECTRO ARCOS ICP-OES仪器进行ICP分析。
所述整体式催化剂包括载体和负载于载体上的活性物质；
所述活性物质包括包裹四氧化三钴颗粒的氮掺杂碳纳米线。
所述整体式催化剂的制备方法包括以下步骤：
S100，溶液的制备：将Co(NO 3) 2与含氮、碳化合物按一定比例混合后加水配成溶液；其中，所述Co(NO 3) 2与含氮、碳化合物摩尔 比为1:1.5～1:5。
较佳地，作为一种可实施方式，含氮、碳化合物为尿素和乙二胺四乙酸四钠中的一种或两种。
本申请中，对于所制备的溶液的浓度没有特殊限定。为了制备出优异性能的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂，增强其催化稳定性，延长使用寿命，较佳地，Co(NO 3) 2与水的摩尔比为1:600～1:1200。
S200，水热反应：将步骤S100中得到的溶液置于反应釜中，加入泡沫金属或泡沫碳或碳纤维布等载体，于110℃～160℃下保温8h～24h，洗涤、干燥后得到前驱体。
步骤S200中，对于所加泡沫金属或泡沫碳或碳纤维布等载体没有特殊限定。为了制备出均匀的催化剂，提高催化效率，较佳地，泡沫金属或泡沫碳或碳纤维布等载体规格满足于可浸没于溶液中。
本步骤通过水热反应得到前驱体，其中水热温度为110℃～160℃，热时间为8h～24h。
反应得到的前驱体表面覆盖有少量沉淀，为去除沉淀，需进行洗涤操作，较佳地，洗涤方法为：将所述前驱体依次使用水和乙醇冲洗2～3次。
前驱体冲洗完后，为去除残留的水和乙醇，需进行烘干操作。较佳地，干燥条件为：60℃～80℃下干燥8h～12h。
S300，碳化过程：将步骤S200中得到的前驱体置于加热炉中，通入保护气体，于300℃～400℃下保温0.5h～1h，冷却后即可得到整体式氮掺杂碳包裹四氧化三钴纳米线催化剂。
本步骤通过碳化过程得到目标整体式氮掺杂碳包裹四氧化三钴纳米线催化剂，其中，为方便保护气体的通入，加热炉优选为内置石英管或刚玉管的管式炉，保护气体优选为氮气、氩气和氦气中的一种或多种。保护气体的流量不宜过大，其流量优选为100mL/min～180mL/min。该流量下，既能防止产物的烧蚀，又能保证产物的纯度，进而提高了产物的物理化学性能。
步骤S300中，加热方式采用一步升温方式，为保证产物质量， 加热速度不宜过快，较佳地，加热炉的温度控制过程为：以4℃/min～8℃/min的速度由室温升温至300℃～400℃，保温0.5h～1h后，以2℃/min～3℃/min的速度冷却至室温。
本申请中，含氮、碳化合物的作用是同时提供N源和C源，形成掺杂氮的碳包裹层，减少酸碱对钴的腐蚀，延长催化剂使用寿命。
需要说明的是，在最终得到的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂中，Co元素的负载量和N原子的掺杂浓度可通过初始时各原料的比例进行调控。
本发明的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂的制备采用简单的操作方法，对设备和技术要求低，使用的原料为常用的化工原料，成本较低；本发明方法得到的催化剂中N原子分布均匀，
Co元素负载量和N原子掺杂浓度可调，从而能满足不同条件下的应用；且本发明得到的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂具有较高含量的导电性好的掺杂碳，与四氧化三钴纳米线共同作用，使催化剂具有高导电性和较长的使用寿命；此外，该方法制备的整体式催化剂与纳米粉体催化剂相比，传质孔道多，使用后更容易与催化产物分离。
实施例1
(1)在烧杯中加入0.584g Co(NO 3) 2·6H 2O、0.6g尿素、36mL去离子水，室温下搅拌均匀。其中，Co(NO 3) 2与尿素摩尔比为1:5，Co(NO 3) 2与水的摩尔比为1:1000。
(2)将步骤(1)制备的溶液转移至100mL反应釜中，加入泡沫镍载体，使其浸没于溶液中，放入烘箱中于120℃下反应8h，取出后依次用水和乙醇冲洗2次，置于烧杯中，放入烘箱中于60℃下干燥12h，得到前驱体。
(3)将步骤(2)得到的前驱体置于管式炉的石英舟里，密封后通入高纯氮气作为全程保护气，其中氮气的流量为150mL/min；通气30min后以5℃/min的速度升温至350℃，保温0.5h后，以3℃/min的速度冷却至室温，得到的产物即为泡沫镍上生长的整体式氮掺杂碳 包裹四氧化三钴纳米线催化剂，记为样品1。
实施例2
(1)在烧杯中加入0.584g Co(NO 3) 2·6H 2O、0.2g尿素、36mL去离子水，室温下搅拌均匀。其中，Co(NO 3) 2与尿素摩尔比为1:1.67，Co(NO 3) 2与水的摩尔比为1:1000。
(2)同实施例1
(3)同实施例1，得到的样品记为样品2。
与实施例1相比，本实施例所使用的原料中尿素的质量发生了变化，其余制备条件均未改变，随着尿素质量的减少，最终得到的催化剂的氮掺杂碳包裹层变薄，氮掺杂量降低。
实施例3
(1)同实施例1
(2)将步骤(1)制备的溶液转移至100mL反应釜中，加入泡沫镍载体，使其浸没于溶液中，放入烘箱中于140℃下反应8h，取出后依次用水和乙醇冲洗2次，置于烧杯中，放入烘箱中于60℃下干燥12h，得到前驱体。
(3)同实施例1，得到的样品记为样品3。
与实施例1相比，本实施例所使用的水热反应的温度发生了变化，其余制备条件均未改变，随着水热反应温度的升高，最终得到的氮掺杂碳包裹四氧化三钴纳米线催化剂的纳米线直径变大。
实施例4
(1)在烧杯中加入0.3g Co(NO 3) 2·6H 2O、0.124g尿素、20mL去离子水，室温下搅拌均匀。其中，Co(NO 3) 2与尿素摩尔比为1:2，Co(NO 3) 2与水的摩尔比为1:1078。
(2)将步骤(1)制备的溶液转移至100mL反应釜中，加入碳纤维布，使其浸没于溶液中，放入烘箱中于120℃下反应12h，取出后依次用水和乙醇冲洗2次，置于烧杯中，放入烘箱中于60℃下干 燥12h，得到前驱体。
(3)将步骤(2)得到的前驱体置于管式炉的石英舟里，密封后通入高纯氩气作为全程保护气，其中氮气的流量为120mL/min；通气40min后以5℃/min的速度升温至350℃，保温0.5h后，以2℃/min的速度冷却至室温，得到的产物为碳纤维布上生长的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂，记为样品4。
实施例5
(1)在烧杯中加入0.584g Co(NO 3) 2·6H 2O、0.8g Na 4EDTA·4H 2O、36mL去离子水，室温下搅拌均匀。其中Co(NO 3) 2与Na 4EDTA·4H 2O摩尔比为1:1.77，Co(NO 3) 2与水的摩尔比为1:1000。
(2)将步骤(1)制备的溶液转移至100mL反应釜中，加入泡沫碳载体，使其浸没于溶液中，放入烘箱中于130℃下反应8h，取出后依次用水和乙醇冲洗2次，置于烧杯中，放入烘箱中于60℃下干燥12h，得到前驱体。
(3)将步骤(2)得到的前驱体置于管式炉的石英舟里，密封后通入高纯氩气作为全程保护气，其中氮气的流量为140mL/min；通气30min后以5℃/min的速度升温至400℃，保温0.5h后，以3℃/min的速度冷却至室温，得到的产物即为泡沫碳上生长的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂，记为样品5。
实施例6
将样品1～样品5以及将从载体上机械剥离的氮掺杂碳包裹四氧化三钴纳米粉体进行XRD测试。图1为样品1以及从泡沫镍上机械剥离的氮掺杂碳包裹四氧化三钴纳米线粉体、以及未剥离前样品的XRD谱图，由图可知，剥离的粉体样品在2-Theta角为31.27(2 2 0)、36.85(3 1 1)、44.81(4 0 0)、59.36(5 1 1)、65.24(4 4 0)处有较明显的衍射峰，归属于四氧化三钴的特征峰，而未剥离的样品由于泡沫镍上生长的氮掺杂碳包裹四氧化三钴纳米线层XRD信号远不如基底金属镍的信号强度，因此整体体现为泡沫镍的信号，仅在 2-Theta＝36.85处有弱信号。
样品2～样品3以及将从泡沫镍上机械剥离的氮掺杂碳包裹四氧化三钴纳米粉体进行XRD测试，与图1仅有峰强度的差别，特征峰均一致。
样品4以及将从碳纤维布上机械剥离的氮掺杂碳包裹四氧化三钴纳米粉体进行XRD测试，剥离的氮掺杂碳包裹四氧化三钴纳米粉体与图1中剥离的氮掺杂碳包裹四氧化三钴纳米粉体仅有峰强度的差别，特征峰均一致。
样品5以及将从泡沫碳上机械剥离的氮掺杂碳包裹四氧化三钴纳米粉体进行XRD测试，剥离的氮掺杂碳包裹四氧化三钴纳米粉体与图1中剥离的氮掺杂碳包裹四氧化三钴纳米粉体仅有峰强度的差别，特征峰均一致。
实施例7
将样品1～样品5以及将从载体上机械剥离的氮掺杂碳包裹四氧化三钴纳米粉体进行SEM和TEM测试。图2为实施例1得到的泡沫镍上生长的整体式氮掺杂碳包裹四氧化三钴纳米线催化剂的扫描电镜图，由图可见催化剂的微观结构为松枝状。图3为本实例得到的机械剥离的氮掺杂碳包裹四氧化三钴纳米线催化剂的透射电镜图，从图中可知，该催化剂纳米线直径为50nm左右，长度大于500nm。
样品2～样品3以及将从载体上机械剥离的氮掺杂碳包裹四氧化三钴纳米粉体的SEM图和TEM图与样品1相似，仅有纳米线直径的区别。
样品4～样品5以及将从载体上机械剥离的氮掺杂碳包裹四氧化三钴纳米粉体的SEM图和TEM图与样品1相似，仅有载体的区别与纳米线直径的区别。
实施例8
将样品1～样品5从载体上机械剥离的氮掺杂碳包裹四氧化三钴纳米粉体进行X光电子能谱测试。图4为实施例1中样品1的X光 电子能谱图，结果表明，该催化剂表面各元素百分含量分别为C(37.65at％)、N(1.08at％)、Co(7.27at％)以及载体镍元素，电感耦合等离子体质谱仪ICP测定的总体钴含量为20.1at％，因此综上证明钴实际上以Co 3O 4形式被掺氮碳层包裹。
将样品1～样品5从载体上机械剥离的氮掺杂碳包裹四氧化三钴纳米粉体进行STEM测试，得到STEM元素分布图。图5为实施例1中样品1的STEM元素分布图，表明，碳元素、氮元素、氧元素和钴元素均匀分布。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (14)

  1. 一种整体式催化剂，其特征在于，所述整体式催化剂包括载体和负载于载体上的活性物质；
    所述活性物质包括包裹四氧化三钴颗粒的氮掺杂碳纳米线。
  2. 根据权利要求1所述的整体式催化剂，其特征在于，所述活性物质原位生长于所述载体表面。
  3. 根据权利要求1所述的整体式催化剂，其特征在于，所述活性物质的形貌为包裹四氧化三钴颗粒的氮掺杂碳纳米线形成的枝状。
  4. 根据权利要求1所述的整体式催化剂，其特征在于，所述载体选自泡沫金属、泡沫碳、碳纤维布中的至少一种。
  5. 根据权利要求1所述的整体式催化剂，其特征在于，所述四氧化三钴颗粒的粒径为3～10nm；
    所述纳米线的直径为40～60nm；
    所述纳米线的长度为500～2000nm。
  6. 根据权利要求1所述的整体式催化剂，其特征在于，所述活性物质中氮元素的摩尔含量为0.5％～2％；所述活性物质中碳元素的摩尔含量为20％～40％；所述活性物质中钴元素的摩尔含量为5％～10％。
  7. 一种整体式催化剂的制备方法，其特征在于，包括以下步骤：
    S100：获得含有钴源、氮源、碳源的水溶液；
    S200：将载体浸没于所述水溶液中，加热反应，得到前驱体；
    S300：将所述前驱体在保护气体的气氛中，加热反应，得到所述整体式催化剂。
  8. 根据权利要求7所述的整体式催化剂的制备方法，其特征在于，
    步骤S100中所述水溶液中钴源中的钴元素、氮源中的氮元素、碳源中的碳元素与水的摩尔比为1:3～10:1.5～50：600～1200。
  9. 根据权利要求7所述的整体式催化剂的制备方法，其特征在于，
    所述钴源选自CoF 2、CoCl 2、CoBr 2、CoI 2、CoCO 3、Co(NO 3) 2、CoSO 4中的至少一种；
    所述氮源选自尿素、乙二胺四乙酸四钠中的至少一种；
    所述碳源选自尿素、乙二胺四乙酸四钠中的至少一种。
  10. 根据权利要求7所述的整体式催化剂的制备方法，其特征在于，步骤S200中所述加热反应的温度为110℃～160℃，加热反应的时间为8～24h。
  11. 根据权利要求7所述的整体式催化剂的制备方法，其特征在于，步骤S200为：将载体浸没于所述水溶液中，加热反应，洗涤，干燥，得到前驱体；
    所述洗涤为：依次使用水和乙醇冲洗2～3次；
    所述干燥条件为：60℃～80℃下干燥8h～12h。
  12. 根据权利要求7所述的整体式催化剂的制备方法，其特征在于，步骤S300中所述保护气体选自氮气、氩气、氦气中的至少一种；
    所述保护气体的流量为100mL/min～180mL/min。
  13. 根据权利要求7所述的整体式催化剂的制备方法，其特征在于，步骤S300中所述加热反应的温度为300℃～400℃，加热反应的时间为0.5h～1h。
  14. 根据权利要求7所述的整体式催化剂的制备方法，其特征在于，
    步骤S300中所述加热反应的条件为：以4℃/min～8℃/min的速度由室温升温至300℃～400℃，保温0.5h～1h后，以2℃/min～3℃/min的速度冷却至室温。
PCT/CN2020/095322 2019-09-20 2020-06-10 一种掺氮碳包裹四氧化三钴纳米线整体式催化剂及其制备方法 WO2021051896A1 (zh)

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