WO2016043396A1 - Procédé de préparation de graphène dopé à l'azote et graphène dopé à l'azote ainsi préparé - Google Patents

Procédé de préparation de graphène dopé à l'azote et graphène dopé à l'azote ainsi préparé Download PDF

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WO2016043396A1
WO2016043396A1 PCT/KR2015/003464 KR2015003464W WO2016043396A1 WO 2016043396 A1 WO2016043396 A1 WO 2016043396A1 KR 2015003464 W KR2015003464 W KR 2015003464W WO 2016043396 A1 WO2016043396 A1 WO 2016043396A1
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nitrogen
graphene
doped
compound
doped graphene
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후이관남
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부산대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties

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  • the present invention relates to a method of preparing nitrogen-doped graphene, wherein carbon and nitrogen are supplied from a carbon compound and an amine compound, and Fe 2+ ions are used as graphene growth catalysts to control the content of pyridine-like arrays.
  • the present invention relates to a method for preparing nitrogen doped graphene, which has an improved content of nitrogen and shows excellent electrochemical activity for redox reactions.
  • Graphene is a hexagonal two-dimensional monolayer composed of carbon atoms. It is a 0-dimensional fullerene, a tube-shaped one-dimensional structure of carbon nanotubes, and 3 Due to the structural difference from graphite having a dimensional structure, graphene has excellent electrical, mechanical, and chemical properties, and has excellent conductivity. In other words, since graphene has a 2-dimensional ballistic transport property, the mobility of charge in graphene is very high, and thus the charge mobility of 15,000 cm 2 V -1 s -1 or higher is maintained at room temperature. see.
  • graphene has the advantage that it is very easy to process one-dimensional, two-dimensional nanopatterns made of carbon, which is a relatively light element, and it is possible to control semiconductor-conductor properties as well as the chemical bonding of carbon.
  • the diversity also enables the manufacture of a wide range of functional devices, including sensors and memories.
  • the nitrogen-doped graphene has a high surface area, excellent electrical conductivity, and a conjugation of the ⁇ -optal of graphene with the lone pair of nitrogen.
  • Chemical vapor deposition is a method in which gaseous components react chemically to form a graphene thin film on the surface of a substrate on which a specific metal is deposited. It is carried out under nitrogen urea and is the most common method of in situ doping with nitrogen. This manufacturing method provides relatively low defects of graphene, but the process temperature must be maintained at a high temperature in order to supply the raw materials of graphene to be manufactured in gaseous form. There is a need for a process that is only possible on metal-deposited surfaces and that the grown graphene must be transferred back to the desired substrate. In addition, it is difficult to grow the size by growing graphene.
  • nitrogen-doped carbon materials may be prepared through thermal decomposition of transition metal macrocyclic compounds, but these compounds are expensive or difficult to synthesize.
  • the present invention provides a nitrogen-doped graphene prepared by the above method as another problem.
  • Another object of the present invention is to provide an electrochemical energy device containing the nitrogen-doped graphene.
  • a second step of forming a compound including carbon atoms, nitrogen atoms and Fe 2+ ions by adding and stirring a solution containing Fe 2+ ions to the mixture solution containing carbon atoms and nitrogen atoms, and then obtaining them ;
  • nitrogen-doped graphene manufacturing method of the present invention carbon and nitrogen for the production of nitrogen-doped graphene from a carbon compound and an amine compound are supplied, in particular by using melamine as a nitrogen source, It is possible to improve the content of nitrogen, and furthermore, to control the content of the pyridine-like arrangement shows excellent electrochemical activity for the Oxygen Reduction Reaction (ORR).
  • ORR Oxygen Reduction Reaction
  • the added Fe 2+ ions function as growth catalysts for growing nitrogen-doped graphene and are formed as Fe substrates during the entire process of forming nitrogen-doped graphene, the nitrogen atoms to be doped By stabilizing them, it is possible to overcome the limitations of the substrate surface to form nitrogen-doped multilayered graphene and increase the size of the graphene.
  • the multilayered graphene can be prepared as a protein or a carbohydrate, it can be widely used in the field of electrochemical energy devices.
  • FIG. 1 is a schematic view showing a method for preparing a nitrogen doped multilayer graphene according to the present invention.
  • Figure 2 shows (a) TEM image, (b) AFM image, (c) XPS graph, (d) Raman spectrum of N-MLG-45min according to an embodiment of the present invention.
  • FIG. 3 shows an XPS graph according to an embodiment of the present invention.
  • A XPS graph for nitrogen of N-MLG-45min
  • b XPS graph for nitrogen of N-MLG-45min, N-MLG-90min, N-MLG-120min
  • Figure 4 shows the Raman spectrum of N-MLG-45min, N-MLG-90min, N-MLG-120min of the present invention.
  • Figure 5 is a linear scan voltage-current curve according to an embodiment of the present invention, (b) rotating disk voltage-current curve, (c) Koutecky-Levich graph, (d) the linear scan voltage according to the Fe content -Shows the current curve.
  • the present invention relates to a method for preparing nitrogen-doped graphene capable of improving nitrogen content and growing graphene, according to an aspect of the present invention.
  • a second step of forming a compound including carbon atoms, nitrogen atoms and Fe 2+ ions by adding and stirring a solution containing Fe 2+ ions to the mixture solution containing carbon atoms and nitrogen atoms, and then obtaining them ;
  • the first step is to prepare a mixture solution containing carbon atoms and nitrogen atoms by adding a carbon compound and an amine compound to an acidic solution and heating and stirring to decompose the carbon compound, wherein the carbon compound is a protein, a monosaccharide, a disaccharide, an oligosaccharide. It is characterized in that any one selected from the group consisting of polysaccharides and combinations thereof, more preferably characterized in that the protein is a milk protein.
  • the amine compound is melamine (C 3 H 6 N 6 ), ammonia (NH 3 ), hydrazine (NH 2 NH 2 ), pyridine (C 5 H 5 N), pyrrole (C 4 H 5 N), acetonitrile (CH 3 CN), triethanolamine (C 6 H 15 NO 3 ), aniline (C 6 H 7 N) 3-aminobenzoic acid (C 7 H 7 NO 2 ), 4-aminobenzoic acid, 3- (4-aminophenyl ) Benzoic acid (C 13 H 11 NO 2 ), 4- (4-aminophenyl) benzoic acid, 4- (3-aminophenyl) benzoic acid (C 13 H 11 NO 2 ), 5-aminoisophthalic acid (C 8 H 7 NO 4 ), 3- (4-aminophenoxy) benzoic acid (C 13 H 11 NO 3 ), 4- (4-aminophenoxy) benzoic acid, 3,4-diaminobenzoic acid (C 7 H 8 N 6
  • the base on which the Fe 2+ ions to be added in the second step can be stirred
  • a protein and a carbohydrate a group consisting of monosaccharides, disaccharides, oligosaccharides, polysaccharides, and combinations thereof
  • the protein and carbohydrates become a promising carbon source that can be widely applied in the field of electrical energy devices.
  • the amine compound melamine as a nitrogen source as described above, it is possible to form a nitrogen-doped multilayered graphene, which significantly improves the nitrogen content in the preparation of the nitrogen-doped graphene.
  • a protein including an amine group among carbon compounds used as a carbon source of nitrogen doped graphene it can also be used as a source of nitrogen doped.
  • the mixture solution containing the carbon atom and the nitrogen atom and the solution containing Fe 2+ ions are stirred under nitrogen protection.
  • the solution containing Fe 2+ ions is a solution further comprising an ammonium group, and supplies Fe 2+ ions to a mixture solution containing carbon and nitrogen atoms formed in the first step, as well as being doped. It can be a source of nitrogen atoms.
  • the added amount of Fe does not participate in the reaction, but prevents Fe 2+ ions from being oxidized to Fe 3+ ions.
  • the third step is to form a Fe substrate by heat-treating the compound obtained in the second step in a nitrogen atmosphere
  • the heat treatment of the third step is 850 ⁇ 1200 °C under nitrogen atmosphere for 45-120 minutes
  • the nitrogen content of the nitrogen-doped graphene is improved, and the multilayer nitrogen graphene formed forms a pyridine-like array 30. It includes ⁇ 35% to improve the function as a catalyst of the redox reaction.
  • the Fe substrate formed in the third step is similar to the function of the substrate in the CVD manufacturing method, but unlike the CVD manufacturing method, the Fe substrate of the present invention is formed during the entire process of forming the nitrogen-doped graphene Fe 2+ ions contribute to the stabilization of the nitrogen atoms doped together with the function as a growth catalyst to grow nitrogen doped graphene. That is, the size of nitrogen doped multilayer graphene can be grown by overcoming the limitation of the limited substrate surface, including nitrogen doped monolayer graphene and nitrogen doped multilayer graphene.
  • the heat treatment reaction of the third step is carried out in a nitrogen atmosphere, it can be used also as a source of nitrogen to be doped.
  • the fourth step is a step of forming a nitrogen-doped graphene by diffusing carbon atoms and nitrogen atoms included in the compound on the Fe substrate by cooling after the third step.
  • the nitrogen-doped graphene is characterized in that the nitrogen-doped multilayer graphene.
  • the doped nitrogen is composed of pyridinic-N, pyrrolic-N, and graphite-N, graphitic-N. Pyridine-like arrangements contain 30-35%.
  • the amine compound is more preferably melamine.
  • the nitrogen-doped graphene manufacturing method of the present invention may further include a fifth step of removing the Fe substrate by reacting by adding an acid after the last fourth step.
  • the Fe substrate prepared in the fourth step is not removed.
  • the redox reaction is similar to that of the nitrogen doped graphene from which the Fe substrate prepared by further including the fifth step is removed, but the activity of the redox reaction is reduced. .
  • the nitrogen-doped graphene from which the Fe substrate is removed by further including the fifth step.
  • a nitrogen doped graphene characterized in that produced by the above-described method.
  • the present invention provides an electrochemical energy device containing the prepared nitrogen doped graphene.
  • the electrochemical energy device containing nitrogen-doped graphene includes a fuel cell and metal-air-batteries.
  • the solid obtained as above was dried in vacuo and then heat treated at 1000 ° C. under a nitrogen atmosphere.
  • a nitrogen-doped multilayer graphene soot was prepared by treatment with HCl (2.0 mol / L, 200 mL) at 80 ° C.
  • the prepared nitrogen-doped multilayer graphene soot is dispersed in water by centrifugation, and the upper centrifuge is obtained through filtration, washing, and drying, so that about 2 g of nitrogen-doped multilayer graphene is obtained. Obtained.
  • the manufacturing process of the nitrogen doped multilayer graphene according to the present embodiment is shown in FIG.
  • the reaction was heat-treated at 1000 ° C. under nitrogen atmosphere for 45 minutes, 90 minutes, and 120 minutes, respectively. Leveling was at N-MLG-45min, N-MLG-90min, N-MLG-120min. However, the samples were treated with HCl at 80 ° C. for 6 hours after the Fe substrate was prepared to remove the Fe substrate.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 Fe substrate manufacturing step Heat treatment (1000 °C) Reaction time (min) 45 60 90 Fe removal reaction (HCl treatment time) 0 3 6 0 6 0 6
  • TEM images were measured using a high-resolution JEOL 2000F TEM system operating on LaB6 filaments at 2000 kV.
  • Atomic force microscopy (AFM) images were measured using a Nanonavi Probe Station and Seiko SPA 400 in tapping mode.
  • X-ray Photoelectron Spectroscopy (XPS), ESCALAB250 from VG Scientific Ltd, was used to measure the valence electron state and binding energy of the samples prepared from the above examples, and graphene surface materials were selected.
  • Raman spectra were measured using a micro-Raman spectrometer (Renishaw, InVia). The laser beam excited at the 514 nm wavelength was focused by the objective lens, with a numerical aperture of 0.75 on the sample about 1 ⁇ 2 .
  • TGA was measured using a Pyris Diamon TG / DTA thermogravimetric analyzer from Perkin-Elmer. The sample was measured by heating to 10 ° C. min ⁇ 1 from room temperature to 900 ° C. in air.
  • the polarization curve for the redox reaction was measured using a Rotating Disc Electrodes (RDE) while controlling the speed with Metrohm 628-10unit in 1.0M KOH solution.
  • RDE Rotating Disc Electrodes
  • Figure 2 shows the (a) TEM image, (b) AFM image, (c) XPS graph, (d) Raman spectrum for N-MLG-45min, through which the nitrogen doped multilayer graphene was formed. there was.
  • the surface material of the nitrogen-doped multilayer graphene is represented by carbon, nitrogen, and oxygen
  • the Fe atom only promotes the growth of graphene but is not a component.
  • the Raman spectrum of FIG. 2 (d) shows G-band, D-band, and 2D-band, graphene doped with nitrogen was formed.
  • Figure 3 (a) is an XPS graph for N (N) of N-MLG-45min
  • Figure 3 (b) is a nitrogen for N-MLG-45min, N-MLG-90min, N-MLG-120min respectively
  • the XPS graph is shown, through which the doped nitrogen type and its intensity and binding energy can be analyzed, and these data are summarized in Table 3 below.
  • N1 is a pyridinic-N with pyridine-like arrangement
  • N2 is a pyrrolic-N with pyrrole-like arrangement
  • N3 represents a nitrogen-like graphitic-N with graphite-like arrangement.
  • the nitrogen doped multilayer graphene of the present invention comprises three types of nitrogen doping, N1 (pyridinic-N), N2 (pyrrolic-N), N3 (graphitic-N), nitrogen-doped multilayer
  • N1 pyridinic-N
  • N2 pyrrolic-N
  • N3 graphitic-N
  • nitrogen-doped multilayer the total nitrogen content percentage including the three types of nitrogen doping decreases from 7.41% to 3.45% as the heat treatment time increases. It is believed that some nitrogen atoms are separated from the carbon plane as the heat treatment time increases.
  • each of the three types of nitrogen with respect to the total doped nitrogen content hardly changes the case of N2 (pyrrolic-N), but the content of N1 (pyridinic-N) From 34.6% to 24.8%, N3 (graphitic-N) content was found to increase from 34.8% to 45.1%. It is believed that pyridinic-N (N1) nitrogen type is changed to N3 (graphitic-N) as the heat treatment time increases at high temperature (1000 ° C).
  • the binding energy of each doped nitrogen type was found to be the lowest as 398.7eV when N1 (pyridinic-N), 402.0eV when the N3 (graphitic-N).
  • N1 (pyridinic-N) nitrogen type the nitrogen atom binds two carbon atoms and gives the ⁇ -electron, the lone pair, as an aromatic ⁇ system
  • N3 (graphitic-N) nitrogen type the nitrogen atom has three nitrogen atoms.
  • the binding force of the N3 nitrogen type was higher because the bonding energy of the N3 nitrogen type was higher than that of the N1 nitrogen type because it is bonded to the carbon atom and there is no lone pair around the nitrogen atom.
  • the nitrogen type (pyridinic-N) having a pyridine-like arrangement decreases and the nitrogen type (graphitic-N) having a graphite-like arrangement increases.
  • the heat treatment time was increased, it was determined that pyridine pseudo-array nitrogen (pyridinic-N) was converted into graphite pseudo-array nitrogen (graphitic-N), and thus the value of I G / I D was increased.
  • FIG. 5 (a) contains N-MLG-45min, N-MLG-90min, N-MLG-120min, CNTs, undoped graphene and 20wt% Pt in oxygen saturated 1.0 M KOH solution
  • the linear sweep voltammetry of Pt / C is shown.
  • the starting potential of N-MLG-45min is -0.05V
  • the CNTs starting potential is -0.25V.
  • the graphene (graphene) starting potential was found to be high compared to -0.24V.
  • N-MLG-45min (-0.05V) is slightly lower than the starting potential of Pt / C catalyst (0.01V), but is higher than most catalyst starting potentials not based on Pt, and moreover, N-MLG- The current density of 45 min was similar to that of the Pt / C catalyst.
  • N-MLG-45min which is nitrogen-doped multilayer graphene in Figure 5 (a)
  • the total nitrogen content of each is similar to 7.41%, 6.13%, but N-MLG-45min
  • the half-wave potential of -0.18V was higher than that of N-MLG-90min, compared to -0.23V.
  • the half-wave potential value of N-MLG-45min is higher than N-MLG-90min is the difference in the type of the doped nitrogen, that is, the content of the pyridine pseudo-array nitrogen (pyridinic-N), pyridine pseudo-array nitrogen (pyridinic-N) is believed to improve the electrocatalytic performance of the redox reaction.
  • the electrocatalytic activity of nitrogen doped multilayer graphene was found to be directly related to the nitrogen content and the ratio of pyridinic-array nitrogen (pyridinic-N) to the total doped nitrogen.
  • Figure 5 (b) shows a linear scan voltage-current curve using a rotating disk electrode, the voltage for N-MLG-45min with different rotational speed using the rotating disk electrode in 1.0M KOH solution saturated with O 2 -Shows the current curve.
  • Rotating Disc Electrodes were analyzed using Koutecky-Levich equation.
  • J K and J L are kinetic current density and diffusion limit current density, respectively.
  • the voltage-current was measured under various RDE rpms (800, 1200, 1600, 2000 rpm) to obtain n values through J K and B values in FIG. 5 (c).
  • the current remains almost constant in the potential range of 0.090V to 0.20V.
  • FIG. 5 (c) a constant value of the electron potential for the redox reaction is shown at different electrode potentials of ⁇ 0.2 V, ⁇ 0.25 V, and 0.40 V.
  • FIG. 5 (c) a constant value of the electron potential for the redox reaction is shown at different electrode potentials of ⁇ 0.2 V, ⁇ 0.25 V, and 0.40 V.
  • the number n of electrons transferred through Koutecky-Levich equations (1) to (3) is measured to be about 4, which is the target product H 2 O directly without passing through H 2 O 2 as an intermediate in the reduction reaction of oxygen.
  • the reaction proceeds to obtain a total of four electron transfer means. This can be confirmed through the following schemes (4) to (8).
  • the oxygen reduction proceeds by transferring four electrons in the oxygen reduction for N-MLG-45min, the oxygen molecules are graphene in an aqueous solvent as shown in Equation (4) After being adsorbed on the sheet, four electrons are transferred as shown in Equations (5) to (8), thereby forming nitrogen-doped multilayer graphene (N-MLG) and H 2 O.
  • N-MLG nitrogen-doped multilayered graphene
  • H 2 O hydrogen peroxide
  • Catalyst (Fe) activity was analyzed to the extent of oxidation according to the Fe content.
  • 5d and 6 show linear scan voltage-current graphs and TGA curves according to Fe content for Examples 1 to 3 (heat treatment time 45 minutes, HCl treatment time 0, 3, 6h), respectively.
  • Example 1 (0h) without Fe removal is similar half-waves.
  • Example 2 (3h) with reduced Fe content is similar half-waves.
  • Example 3 (6h) with Fe removed is similar half-waves.
  • Example 1 (0h) which has similar functionality in the redox reaction but is high in Fe content, caused a reduction in redox activity.
  • Fe contributes to the function of the growth catalyst for growing graphene and the stabilization of the doped nitrogen, but it does not seem to have a functional in the redox reaction.
  • Example 1 (0h) includes Fe at about 26.45 at% in nitrogen-doped graphene, and the Fe is not removed, which is the TGA analysis graph Example 1 (0h) of FIG. 6. 61.7wt%). That is, because the original content of Fe in Example 1 is 67.5wt%.
  • Example 2 Fe was partially removed, and the Fe content was about 33.1 wt%, and in Example 3 (6h), almost all Fe was removed, so that the Fe content was about 5 wt%. In other words, after 6 hours of treatment with HCl, Fe can be seen to be removed.
  • Example 4 the Fe content in each nitrogen doped graphene for Example 4 to Example 7 with or without the removal of Fe and the heat treatment was carried out at 60 ° C or 90 ° C Table 1 with Example 1, Example 3 4 is shown collectively.
  • milk powder can be used as a precursor of a nitrogen-doped graphene (N-MLG) synthesis of a multi-layer structure According to the heat treatment time, it was confirmed that the nitrogen content on the nitrogen-doped multilayer graphene (N-MLG) has a distinct effect on the type of nitrogen and the doped nitrogen.
  • N-MLG nitrogen-doped graphene
  • N-MLG nitrogen-doped multilayered graphene
  • CNTs carbon nanotubes
  • the Fe atoms of the nitrogen-doped multilayer graphene do not act as a synergy catalyst for the redox reaction, but it acts as a catalytic growth material for the formation of nitrogen-doped multilayer graphene to promote and stabilize the N atoms. there was.
  • the content of the doped nitrogen can be improved and further control the content of the pyridine-like arrangement, showing excellent electrochemical activity for the redox reaction It seems to be.
  • Fe can form a graphene-doped multilayer graphene and increase the graphene size while stabilizing the nitrogen atoms functioning and doping as a growth catalyst of graphene, but it is not considered to be functional in the redox reaction.

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Abstract

La présente invention concerne un procédé de préparation de graphène dopé à l'azote, le procédé comprenant : une première étape consistant à préparer une solution mixte contenant des atomes de carbone et des atomes d'azote par l'introduction d'un composé de carbone et d'un composé d'amine dans une solution acide, suivi d'un chauffage, d'une agitation et d'une décomposition thermique ; une deuxième étape consistant à former un composé contenant des atomes de carbone, des atomes d'azote, et du Fe2+, puis à obtenir le composé, le composé étant formé par l'ajout d'une solution contenant du Fe2+ à la solution mixte contenant des atomes de carbone et des atomes d'azote, suivi d'une agitation ; une troisième étape consistant à former un substrat de Fe en traitant thermiquement le composé, qui est obtenu à la deuxième étape, sous une atmosphère d'azote ; et une quatrième étape consistant à former du graphène dopé à l'azote par, après la troisième étape, diffusion des atomes de carbone et des atomes d'azote, qui sont contenus dans le composé, dans le substrat de Fe par refroidissement. Plus préférablement, le procédé comprend en outre une cinquième étape consistant à éliminer, après la quatrième étape, le substrat de Fe en ajoutant un acide pour provoquer une réaction.
PCT/KR2015/003464 2014-09-17 2015-04-07 Procédé de préparation de graphène dopé à l'azote et graphène dopé à l'azote ainsi préparé WO2016043396A1 (fr)

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