JP6308549B2 - Method for producing hollow carbon particles modified with metal oxide nanoparticles - Google Patents

Description

The present invention have a plurality of micro-compartments therein, a method for manufacturing a modified mosquitoes Bon grain member at nanoparticles metallic oxides.

Conventionally, as a carbonaceous material made from carbohydrates such as starch, for example, Patent Document 1 reports that a carbon material generated thermally is activated by using thermal activation or chemical activation. ing. In Non-Patent Document 1, carbon nanoparticles having a specific surface area of 1106 m ² / g are synthesized from a mixture of sucrose and Zn (NO ₃ ) ₂ using a liquid-based spray pyrolysis synthesis technique. Has been reported. Furthermore, it has also been reported in Non-Patent Document 2 that, in the case of starch nanoparticles, fluorescent carbon nanoparticles were prepared by carbonization of natural sago starch formed in advance. Furthermore, according to Non-Patent Document 3, carbon microspheres were made without a catalyst by a common hydrothermal process using various starch materials. Moreover, in nonpatent literature 4, wheat straw was used as a precursor for preparation of a carbon microsphere, and this was hydrolyzed at 190 ° C for 1 hour. A carbon material was prepared using the solution thus obtained as a carbon source. However, there has been no knowledge that carbon fine particles having microcompartments inside can be produced using plant components such as carbohydrates and proteins such as starch and fibers.

An object of the present invention is not just a fine carbon particles, which has a structure that small section therein, the hollow carbon microparticles Oa reflation was raw material gold nanoparticles Shokusan product may be supported by a simple process treatment Ru near it to be manufactured by.

According to one aspect of the present invention , the whole is irregular, having a plurality of compartments that are modified with metal oxide nanoparticles and separated from each other by carbon walls, and having microporous and mesoporous pores. A method for producing hollow carbon particles having a shape, wherein pyrolysis of wheat flour and a metal salt or acetate to obtain hollow carbon particles modified with the metal nanoparticles, and after the pyrolysis, in an oxygen-containing atmosphere A method for producing hollow carbon particles is provided that oxidizes the metal nanoparticles.
Here, the outer diameter before Symbol hollow mosquito Bon particles may be at 100μm or less.
The plurality of sections may have a size of 5 μm to 25 μm.
The surface area may be 400 m ² / g to 1000 m ² / g .
In here, the pyrolysis may be carried out in an inert atmosphere.
The inert atmosphere may be nitrogen, argon or helium.
The thermal decomposition temperature may be 300 ° C. to 2000 ° C.
The heating time may be 1 minute to 5 hours .
In here, the diameter of the nanoparticles may be less than 100 nm.
The nanoparticle diameter may be less than 50 nm.
The front Symbol metals, Ni, Fe, Co, Ag , Au, Pd, may be selected from the group consisting of Cu and Zn.
Further, oxidation of the previous SL metal nanoparticles may be carried out at 300 ° C. or less.

  According to the present invention, hollow carbon particles having a unique structure and having a large surface area and high electrochemical activity are provided. Furthermore, by adding a metal element to the raw material composition, a hollow carbon modified with a metal or its oxide nanoparticles and expected to be used for other applications can be obtained. In addition, in terms of the production method, there is an effect that it can be easily produced by a simple process of baking under a predetermined condition from a material that is easily available as wheat flour and at a low price.

The SEM image of the carbon particle produced in 600 degreeC for 3 hours in inert atmosphere. The SEM image of the carbon particle produced in 600 degreeC for 3 hours in inert atmosphere. SEM image of carbon particles prepared in an inert atmosphere at 900 ° C. for 3 hours. SEM image of carbon particles prepared in an inert atmosphere at 900 ° C. for 3 hours. The SEM image of the carbon particle produced in 1000 degreeC 3 hours in inert atmosphere. The SEM image of the carbon particle produced in 1000 degreeC 3 hours in inert atmosphere. The figure which shows the thermogravimetric analysis result of wheat flour (henceforth Wh in a figure) in inert atmosphere. The figure which shows FT-IR of the flour (Wh-powder) and the carbon fine particle with a fine partition produced at 900 degreeC (Wh900). The figure which shows the X-ray diffraction of the carbon microparticle produced at 900 degreeC. The figure which shows the Raman spectrum of the carbon microparticle produced at 900 degreeC. TEM image of carbon fine particles produced at 900 ° C. The TEM image of another magnification of the carbon fine particle produced at 900 degreeC. The figure which shows the nitrogen adsorption (ADS) -desorption (DES) isotherm of the carbon fine particle product with a microcompartment produced at 900 degreeC. The figure which shows the pore diameter distribution of the carbon fine particle product with a microcompartment produced at the said 900 degreeC. The figure which shows the cyclic voltammogram (CV curve) in various scanning speed. The figure which shows the relationship between the calculated specific capacity and scanning speed. SEM image of Ni nanoparticles supported by carbon. SEM image of another magnification of Ni nanoparticles supported on carbon. SEM image of another magnification of Ni nanoparticles supported on carbon. 4A to 4C show XRD patterns of carbon-supported Ni nanoparticles shown in FIGS. The SEM image of Fe nanoparticle-carbon composite. SEM image of Co nanoparticle-carbon composite. SEM image of silver-carbon composite. The figure which shows XRD of a silver-carbon composite_body | complex. SEM image of gold-carbon composite. The figure which shows XRD of a gold-carbon composite_body | complex. The SEM image of a palladium-carbon composite. The figure which shows XRD of a palladium-carbon composite_body | complex. The SEM image of a copper-carbon composite. The SEM image of a zinc-carbon composite.

  According to the present invention, there is provided a metal and / or oxide-carbon composite material in which hollow carbon particles and metal and / or oxide nanoparticles having a unique morphology modify the hollow carbon particles. These composite materials are distinguished by their outstanding thermal, electrical, mechanical, and tribological properties, including but not limited to supercapacitors, magnetic materials, electrical materials, catalysts, catalyst supports and hydrogen storage systems. Application of a variety of advanced technologies.

  By using the present invention, the amount and / or number of s, p, d, f-block elements of the periodic table in the carbon composite material, and thus the metal / oxide, by precisely adjusting the precursor concentration. : Carbon ratio value can be controlled. In most cases, carbon particles are produced having hollow compartments interconnected by thick carbon walls that represent the structure of the activated carbon. Various elemental salts or acetates are mixed with wheat flour in various ratios to produce carbon host-metal / oxide guest structures.

  According to various embodiments of the present invention, the composite material manufacturing method of the present invention can vary the size, shape, and deposition density of the particles on the carbon support according to the stability of the metal salt or acetate. it can. The process temperature (300 ° C. to 2000 ° C.) and time (1 minute to 5 hours) play an important role in the composition, morphology and crystal structure of the final composite (particularly its graphitic order). Play.

  In the method of the present invention, many s-block elements (Mg, Ca, Sr, etc.), p-block elements (Sn, Sb, Ga, etc.), d-block elements (Ti, V, Mn, Fe, Co, Ni) , Cu, Zn, Ru, Pt, Pd, Ag, Au, W) and f-block elements (Sm, Eu, Gd, etc.) and in situ coating or modifying the carbon surface to produce various new structures Is done. Such coated / modified elemental particles are usually made in their metal form, but can also be in metal form or oxidized by controlling the atmosphere in the reaction chamber when carrying out the method of the invention. It can also be produced in physical form. This metal / oxide-carbon composite is usually produced in a short time and at a relatively low temperature. That is, the coated / modified metal nanoparticles can be oxidized in the air (or other oxygen-containing atmosphere) at a relatively low temperature (300 ° C. or lower). The advantage of this method is that such metal nanoparticles can be oxidized while staying on the carbon surface.

The filled, modified or coated nanoparticles, plates and rods have a diameter of 100 nm, usually between 1 nm and 50 nm, on the voids, pores or surface of the large surface area carbon particles. The shape of the modified particles depends on the precursor and processing parameters. In the method of the present invention, the temperature is varied between 300 ° C. and 2000 ° C. in an inert (N ₂ , Ar, He) or air (oxygen) atmosphere, resulting in a unique carbon support structure.

  Hereinafter, the present invention will be described in more detail with reference to examples. It should be noted that these examples are not intended to limit the invention, but are described below to assist in understanding the invention.

[Example 1: Hollow carbon nanoparticles]
The SEM image shown in FIG. 1a is an irregularly shaped carbon having a diameter of 5 to 100 μm, produced over 3 hours at 600 ° C. in an inert nitrogen atmosphere using whole wheat as the solid powder raw material. Showing particles. In these carbon particles, an opening in which minute sections of 5 to 25 μm are formed by being separated by a carbon wall is visible on the surface. Smooth surfaces of carbon particles and carbon walls are observed. A number of surface openings and compartments with mostly smooth internal and external morphologies are observed in samples made at 600 ° C, 900 ° C, and 1100 ° C. Such structures are unusual and unique in the field of carbon science.

  FIG. 2a is a graph showing the results of thermogravimetric analysis of flour in an inert atmosphere, showing continuous weight loss from room temperature to 1000 ° C. Gaseous hydrocarbons were removed during the pyrolysis of the flour in an inert atmosphere, after which approximately 40% of the carbon product remained. This means that the process yields a product of generally 40% microcompartmented carbon microparticles in an inert atmosphere. Depending on the reaction conditions, i.e. heating rate, final temperature and holding time of the set temperature, the finely-comparted carbon microparticles are produced in a yield of 30-50% based on the initial raw material used.

  FIG. 2b shows the FT-IR spectrum of wheat flour, where some C—H, C—C, C—O, O—H stretching bonds are evident from solid flour. Many of these stretch bonds disappear after the formation of microcompartmented carbon microparticles at 900 ° C., the formation of pure carbon products and the release of hydrocarbons that cause weight loss. It is confirmed that From this, it can be seen that when the released gas is released from the solid-phase carbon, cavities and compartments are generated, and finally microcompartments are generated.

  FIG. 2c shows X-ray diffraction of carbon microparticles produced at 900 ° C., and the 002 and 101 diffraction lines confirm that the formed carbon microparticles with microcompartments are almost amorphous. This can be further confirmed from the fact that the Raman spectrum of FIG. 2d shows a strong D (random) peak and a weak (graphite) bond. 2e and 2f are TEM images showing carbon particles produced at 900 ° C. at different magnifications. These images show that the formed carbon particles have a porous structure with pores of about 10 nm and are poor in order as graphite, but eventually a large surface area carbon product was obtained. Yes.

FIG. 3a shows nitrogen adsorption-desorption of a microcompartmented carbon microparticle product made at 900 ° C. as a typical example. This isotherm was recorded with an automatic adsorption meter (Quantachrome Instrument, Autosorb-1 in the United States). In the measurement, about 20 mg of a sample was used, and degassing was performed at 120 ° C. for 24 hours prior to the measurement. Adsorption-desorption hot springs were recorded at a liquid nitrogen temperature of 77.35K. This isotherm is close to type III. That is, the material of the present invention exhibits a microposour and mesoporous structure. In the present application, the porous material is classified into microporous (less than 2 nm), mesoporous (2 to 50 nm), and macroporous (greater than 50 nm) according to the average pore diameter. The large nitrogen uptake seen in the low specific pressure region (P / P0 <0.1) is indicative of the microporous structure of the material of the present invention. Furthermore, the mesopore structure is confirmed by the appearance of a small hysteresis loop on the isotherm in the region where the relative pressure is higher. This fact was further confirmed by the corresponding pore size distribution calculated based on the BJH method (FIG. 3b). In FIG. 3b, dp is the particle diameter, Vp is the micropore volume, and dVp / d (dp) on the vertical axis is the derivative of the micropore volume with respect to the particle diameter. The specific surface area of the finely divided carbon microparticles was about 782.5 m ² / g. Judging from the observation of SEM images and the nitrogen adsorption isotherm, it can be concluded that the microcompartmented carbon microparticles produced at 900 ° C. exhibit a bimodal pore architecture. This is very useful for practical applications such as organic dye adsorption and vapor detection.

It is considered that a microporous or mesoporous carbon base material having a large surface area can be a candidate for an electrode material or an electric double layer capacitor. Needless to say, the material of the present invention is one of the good candidates for supercapacitor application due to its excellent surface properties. In this regard, the electrochemical capability of the material of the present invention was examined. FIG. 3c shows a typical example of finely divided carbon microparticles produced at 900 ° C. in an electrolyte of 1 MH ₂ SO ₄ aqueous solution at −0.2 to 1.2 V vs. Cyclic voltammograms (CV) measured at various scanning speeds (5, 10, 20, 50, 80 and 100 mVs ⁻¹ ) in the range of the Ag / AgCl reference electrode are shown. These CV curves show the characteristics of the carbon electric double layer capacitor. Its specific capacitance per weight was about 122.38 F / g at a scanning speed of 5 mVs ⁻¹ . Commercially available activated carbon with a surface area of 1000-2000 m ² / g and a pore size distribution in the range of 2-5 nm has a specific capacitance of 100-120 F / g in organic electrolytes. It is worth noting. On the other hand, the specific capacitance of the fine carbon particles with a microcompartment (surface area of about 782.5 m ² / g) of the present invention is larger than that of a general carbon material. Such large values are thought to be due to the micropore and mesopore bimodal morphology of the microcompartmental skeleton.

[Example 2: Hollow carbon particles modified with nanoparticles]
As will be described below, the addition of desired metals and oxides to the materials of the present invention can further improve electrochemical and other performance and can be used, for example, in the development of technologies related to renewable energy storage. Expected to be.

  4a to 4c show SEM images at various magnifications of carbon microparticles with microcompartments filled with Ni nanoparticles. In this example, wheat flour and nickel (ii) nitrate hexahydrate were mixed at a ratio of 2: 1 and heated in a cubicle at 700 ° C. for 3 hours. <50 nm) metal Ni particles were formed in situ and were constrained on the surface of the finely divided carbon microparticles or modified. By changing the ratio between the metal acetate and flour, the amount of nickel nanoparticles in the composite can be high or low. Thus, the process has the potential to be a candidate approach for adjusting the amount of metal particles for actual application. The XRD pattern of the carbon-Ni composite shown in FIG. 4d showed a strong peak of cubic Ni and a peak of a wide amorphous state of carbon. This confirms that pure nickel particles were formed and covered the surface of the unique carbon structure in situ.

  Similarly, other magnetic materials such as cobalt nanoparticles and iron nanoparticles can be deposited on the inner and outer walls of the carbon compartment, as shown in FIGS. 5a and 5b, respectively. Nanoparticles having a particle size of less than 100 nm can be coated on the inner and outer walls of a large surface area carbon support. It can be seen from this that the magnetic nanoparticles are strongly constrained on the surface of the carbon structure, which indicates that this structure has potential for application to magnetic devices.

  Furthermore, in the method of the present invention, a novel noble metal nanoparticle-carbon composite could be produced very well as shown in FIGS. 6a to 6f. These composites may have beneficial optical, electronic and catalytic properties. FIG. 6a is an SEM image showing a state in which nano-sized silver particles uniformly coat carbon fine particles with fine compartments. The purity of these cubic silver is evidenced by the XRD pattern given in FIG. 6b. In order to obtain such a complex, silver (ii) acetate was homogenized with flour. The pure gold nanoparticles and plates modified on the surface of the support carbon and their XRD patterns are shown in FIGS. 6c and 6d, respectively. Similarly, as shown in FIG. 6e, the inventive process of mixing flour with a precursor of Pd (ii) acetate and heat treating at 700 ° C. results in pure nanosized palladium particles covering the carbon support. . The XRD pattern is shown in FIG.

  By using the method of the present invention, transition metals or their oxides also effectively modify the carbon surface. For example, as shown in FIGS. 7a and 7b, copper nanoparticles and zinc nanoparticles can modify the surface of the carbon particles, respectively. In all cases, the particle diameter of the coated nanoparticles is less than 100 nm.

In summary, the one-step manufacturing method of the present invention produces hollow carbon particles having a large surface area, divided by carbon walls, and having fine compartments filled or modified with functional metal or oxide nanoparticles. Is done. The use of commercial whole wheat flour as a raw material precursor to be a carbon source has not been reported so far in papers. A mixture of a powdered carbon precursor and any one element precursor (salt or acetate) or a combination of a plurality of element precursors (salt or acetate) is contained in a high-temperature cubicle and inert (N ₂ , Ar, He, etc.) Heating in an atmosphere within the range of 300 ° C. to 2000 ° C. results in a unique carbon support structure. When this salt or acetate is not added, hollow pure carbon-supported micro-particulate carbon microparticles having a surface area in the range of 400 to 1000 m ² / g are produced. The resulting porous carbon host-element guest structure contains micropores and mesopores, which leads to large reaction rates and is expected to be used in many applications.

  As described above, the hollow carbon particles of the present invention have a plurality of sections partitioned by carbon walls and a double structure of macroporous and mesoporous, and thus have a large surface area and the surface thereof. It becomes possible to perform modification with nanoparticles having functionality. Therefore, the hollow carbon particles of the present invention are expected to be applied to various fields including supercapacitors, magnetic materials, electrical materials, catalysts, catalyst supports, hydrogen storage systems, and the like.

International Publication No. WO2007 / 114849

Chengwei Wang, Yuan Wang, Jake Graser, Ran Zhao, Fei Gao, and Michael J. O’Connell, ACS Nano, 7, 11156, 2013. Suk Fun Chin, Siti Nur Akmar Mohd Yazid, Suh Cem Pang, Sing Muk Ng, Materials Letters, 2012, 85, 50-52. S. Ratchahat, N. Viriya-empikul, K. Faungnawakij, T. Charinpanitkul, A. Soottitantawat, Sci. J. UBU, 1, 40, 2010. Chen Leishan, Wang Cunjing, Miao Yu, and Chen Gairong, Scientific World Journal. 2013: 146930.

Claims (12)

Modified with metal oxide nanoparticles, and having a plurality of compartments separated by a carbon wall together with the inner part has pores of microporous and mesoporous entirely empty carbon particles child in irregularly shaped A manufacturing method comprising:
Hollow carbon particles obtained by pyrolyzing wheat flour and a metal salt or acetate to obtain hollow carbon particles modified with the metal nanoparticles, and oxidizing the metal nanoparticles in an oxygen-containing atmosphere after the pyrolysis Manufacturing method. Before Symbol outer diameter of the hollow mosquito Bon particles is 100μm or less, the production method of the hollow carbon particle terminal of claim 1. The size of the plurality of compartments is 5Myuemu～25myuemu, method for producing hollow carbon particle terminal of claim 2. Surface area of 1000 m ² / g from 400m ² / g, the production method of the hollow carbon particles child according to any one of claims 1 to 3. The method for producing hollow carbon particles according to claim 1 , wherein the thermal decomposition is performed in an inert atmosphere. The method for producing hollow carbon particles according to claim 5, wherein the inert atmosphere is nitrogen, argon, or helium. The method for producing hollow carbon particles according to any one of claims 1 to 6, wherein the temperature of the thermal decomposition is 300 ° C to 2000 ° C. The method for producing hollow carbon particles according to any one of claims 1 to 7 , wherein the heating time is from 1 minute to 5 hours. The diameter of the nanoparticles is less than 100 nm, the production method of the hollow carbon particles child according to any one of claims 1 to 8. The method for producing hollow carbon particles according to claim 9, wherein the nanoparticles have a diameter of less than 50 nm. Before SL metals, Ni, Fe, Co, Ag , Au, Pd, is selected from the group consisting of Cu and Zn, the production method of the hollow carbon particles child according to any one of claims 1 to 10. Oxidation of prior Symbol metal nanoparticles is carried out at 300 ° C. or less, the production method of the hollow carbon particles according to any one of claims 1 to 11.