WO2006046756A1 - Matière en nitrure de carbone poreux et procédé pour la préparation de celle-ci - Google Patents

Matière en nitrure de carbone poreux et procédé pour la préparation de celle-ci Download PDF

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WO2006046756A1
WO2006046756A1 PCT/JP2005/020149 JP2005020149W WO2006046756A1 WO 2006046756 A1 WO2006046756 A1 WO 2006046756A1 JP 2005020149 W JP2005020149 W JP 2005020149W WO 2006046756 A1 WO2006046756 A1 WO 2006046756A1
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nitrogen
carbon
mcn
porous body
porous
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Japanese (ja)
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Ajayan Vinu
Katsuhiko Ariga
Demitri Golberg
Yoshio Bando
Toshiyuki Mori
Takashi Nakanishi
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National Institute For Materials Science
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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
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

Definitions

  • the present invention relates to a carbon nitride porous body and a method for producing the same, and more specifically, a method for producing a carbon nitride porous body in which the ratio of carbon atoms to nitrogen atoms (CZN ratio) can be easily controlled, and The carbon nitride porous body obtained in this way.
  • CZN ratio ratio of carbon atoms to nitrogen atoms
  • FIG. 10 is a flowchart showing a method for producing a nitrogen-containing carbon-based material according to the prior art. Each process will be described.
  • Step S 1 100 Nitrogen-containing porous metal oxides (for example, porous materials composed of metal oxides and composite metal oxides, such as silica mesoporous materials, zeolites, crosslinked clays, etc.) By introducing an organic compound (for example, an organic compound containing a nitrogen atom, a nitrogen-containing bicyclic compound, an amine, an imine, a nitrile, etc.) and thermally decomposing the nitrogen-containing organic compound, A nitrogen-containing carbon-based material whose skeleton is formed by carbon and nitrogen atoms is deposited in the pores.
  • an organic compound for example, an organic compound containing a nitrogen atom, a nitrogen-containing bicyclic compound, an amine, an imine, a nitrile, etc.
  • a metal oxide porous body is placed in the reaction tube, and heated to a predetermined temperature while introducing an inert gas such as nitrogen or argon into the reaction tube.
  • an inert gas such as nitrogen or argon
  • a nitrogen-containing organic compound in a gaseous state is introduced into the reaction tube while maintaining the heating state, thereby introducing the nitrogen-containing organic compound into the pores of the metal oxide porous body for a predetermined time.
  • Perform the CVD reaction As a result, a nitrogen-containing carbon-based material having a skeleton formed of carbon atoms and nitrogen atoms is deposited in the pores of the metal oxide porous body.
  • Step S 1 2 0 0 A porous body made of a nitrogen-containing carbon-based material is obtained by dissolving and removing the metal oxide porous body.
  • the metal oxide porous body is chemically dissolved using hydrofluoric acid or alkali.
  • a specific surface area of 600 m 2 / g or more, an average pore diameter of 1 to 5 nm, and carbon atoms A nitrogen-containing carbon-based porous material having an atomic ratio of C to N (CZN) of 3.3 3 to 12.5 is obtained.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2004-1 68 58 7 Disclosure of Invention
  • the nitrogen-containing carbon-based porous material described in Patent Document 1 has a higher nitrogen content than the conventional homogeneous porous material, there is a limit in trying to increase the nitrogen content further. It was. For this reason, there were limits to the adjustment of various derived characteristics such as adsorption performance. That is, the method for producing a nitrogen-containing carbon-based porous material described in Patent Document 1 uses a single compound containing both components as a nitrogen source and a carbon source as raw materials, and uses this as a starting material. Therefore, the C / N ratio of the resulting product was determined by the starting material compound, and there were limits to increasing the nitrogen ratio and adjusting the CZN ratio to an arbitrary value.
  • an object of the present invention is to provide a method for easily producing a carbon nitride porous body having an intended nitrogen content.
  • the “carbon nitride” referred to in the present specification is not limited to a material having the chemical formula C 3 N 4, and intends a material in which the ratio of nitrogen atoms to carbon atoms is represented by an arbitrary ratio. Means for solving the problem
  • the method for producing a carbon nitride porous body (MCN) according to the present invention includes a step of mixing a silica porous body, a nitrogen source, and a carbon source, a step of heating a mixture obtained by the mixing step, and the heating A step of removing the porous silica from the reaction product obtained by the step of producing a porous carbon nitride as described above.
  • the porous silica material functions as a template. Specifically, pores selected from the group consisting of MCM-48, SBA-15, KIT-5, and SBA-1 are provided. A porous silica material having a structure communicating with each other can be mentioned and used.
  • the nitrogen source As the nitrogen source, it easily diffuses into the porous silica and is thermally decomposed to form nitride. Although it is not particularly limited as long as it can be produced, a nitrogen-containing compound such as amines or diaryls is preferable. More specifically, one or more selected from the group consisting of aliphatic amines, aromatic amines, ammonia, aliphatic nitriles, aromatic nitriles, nitrogen-containing heterocyclic compounds, and hydrazine are used.
  • the carbon source is not particularly limited as long as it can easily diffuse into the porous silica and can be pyrolyzed to produce a carbide, and preferably includes a halogenated hydrocarbon or a derivative thereof.
  • octalogated hydrocarbon one or more selected from the group consisting of chlorinated hydrocarbon, brominated hydrocarbon, and iodinated hydrocarbon are used.
  • chlorinated hydrocarbon one or more selected from the group consisting of carbon tetrachloride, black mouth form, methylene chloride, chloroform, and dichloromethane are used.
  • brominated hydrocarbon include carbon tetrabromide and bromoform.
  • iodinated hydrocarbon include iodomethane and iodinated tan.
  • the heating step may further include a step of polymerizing the mixture at a first temperature and a step of carbonizing the mixture at a second temperature higher than the first temperature.
  • the polymerization step is preferably performed by heating the mixture at the first temperature for 1 hour to 6 hours, which is selected from a temperature range of 70 to 1550 in the atmosphere.
  • the carbonizing step includes heating the mixture at a second temperature selected from a temperature range of 50.00 to 800 in a nitrogen atmosphere or an inert gas atmosphere for 4 to 8 hours. Is preferred.
  • the removal process of the porous silica is performed by selectively dissolving the porous silica using hydrofluoric acid or an alkaline aqueous solution, and filtering and recovering the reaction product (nitrogen carbon porous body) as an insoluble residue. .
  • a step of washing and drying the reaction product after the removing step may be further included.
  • the ratio (C / N) of the carbon atoms (C) to the nitrogen atoms (N) has a relationship of 0.25 ⁇ C /N ⁇ 3.0 is satisfied, and the carbon atom and the nitrogen atom are a single bond or a double bond, thereby achieving the above object.
  • the specific surface area of the MCN porous body is preferably 50 Om ⁇ / g or more from the viewpoint of improving adsorption characteristics.
  • the pore diameter of the MCN porous body may be 4 nm or more and 10 nm or less.
  • the method for producing a carbon nitride (MCN) porous body according to the present invention includes a step of mixing a silica porous body, a nitrogen source, and a carbon source, a step of heating a mixture obtained by the mixing step, and a step of heating Removing the porous silica from the reaction product obtained by the step. Since a nitrogen source and a carbon source are used separately as starting materials, the amount of nitrogen during charging can be easily controlled. As a result, the carbon nitride porous body obtained by the heating step can have an intended nitrogen content. In addition, a carbon nitride porous body having a desired shape, pore diameter, and specific surface area can be obtained by appropriately selecting a silica porous body as a replica. Since the carbon nitride porous body obtained in this way can contain a larger amount of nitrogen than before, the amount of adsorption can be improved.
  • Fig. 1 Flow chart showing a method for producing a carbon nitride porous material (MCN) according to the present invention.
  • Fig. 2 Schematic diagram of carbon nitride porous material (MCN) according to the present invention
  • FIG. 4 Electron micrographs (a) and (b) and elemental mapping (c) and (d) of MCN obtained in Example 1
  • Fig. 5 Electron energy loss spectrum of MCN obtained in Example 1
  • Fig. 6 Nitrogen absorption of MCN complex (a) and SB A- 15 (b) obtained in Example 1 Diagram showing desorption isotherm
  • Fig. 7 Diagram showing the pore size distribution of the MCN composite (a) and SBA-15 (b) obtained in Example 1
  • Fig. 9 XPS wide spectrum (a) of MCN obtained in Example 1, C ls spectrum (b) of MCN, and N ls spectrum (c) of MCN Flow chart showing a method for producing a nitrogen-carbon material Explanation of symbols
  • FIG. 1 is a flow chart showing a method for producing a carbon nitride porous material (M C N) according to the present invention. Each process will be described.
  • Step S 1 1 0 A porous silica material, a nitrogen source and a carbon source are mixed.
  • the silica porous body means an arbitrary structure made of silica in which pore structures are connected three-dimensionally or two-dimensionally.
  • a structure may have a hexagonal structure, a cubic structure, or an irregular structure.
  • the hexagonal structure is a hexagonal structure in which the pores in the porous silica material are arranged, and includes both a known two-dimensional hexagonal structure and a three-dimensional hexagonal structure.
  • the cubic structure is a cubic structure in which the pores in the porous silica are arranged.
  • Such a porous silica is preferably MCM-48 having a cubic structure, SBA-1, SBA-1 having a structure in which one-dimensional medium-sized pores are connected to fine pores, and pores.
  • the silica porous body may be one kind or a combination of two or more kinds.
  • the nitrogen source is a nitrogen-containing compound, and in particular, may be amines or nitriles.
  • Such a nitrogen-containing compound is preferably at least one selected from the group consisting of aliphatic amines, aromatic amines, ammonia, aliphatic nitriles, aromatic nitriles, nitrogen-containing heterocyclic compounds, and hydrazine.
  • the carbon source is a halogenated hydrocarbon or a derivative thereof.
  • At least one such hydrogen halide is selected from the group consisting of chlorinated hydrocarbons, brominated hydrocarbons and iodinated hydrocarbons. Examples of the chlorohydrocarbon include, but are not limited to, carbon tetrachloride, black mouth form, methylene chloride, chloromethane, or dichloromethane.
  • Brominated hydrocarbons include, but are not limited to, for example, carbon tetrabromide or promoform.
  • the iodinated hydrocarbon can be, for example, iodomethane or iodinated tan, but is not limited thereto.
  • Nitrogen and carbon sources can be adjusted so that the ratio of carbon atom (C) to nitrogen atom (N) (CZN) satisfies the relationship CZN ⁇ 0.25. When the C / N ratio was less than 0.25, a carbon nitride porous body could not be obtained.
  • the CZN ratio can preferably be adjusted in the range of 0.2 5 ⁇ C / N ⁇ 3.0.
  • Step S 1 20 The mixture obtained in Step S 1 10 is heated. As a result, the mixture reacts and a carbon nitride porous body can be obtained. More specifically, the mixture is polymerized at a first temperature and then the mixture is carbonized at a second temperature that is higher than the first temperature. Polymerization is carried out by heating in the atmosphere at a first temperature selected from a temperature range of 70 to 150 for 1 to 4 hours.
  • any heating means such as a hot plate can be used for heating.
  • the nitrogen source in the mixture is polymerized, and the mixture containing the polymerized nitrogen source is refluxed.
  • the mixture is located in the pores of the porous silica material by stirring them. This gives a well-ordered carbon nitride porous body (MCN).
  • Carbonization is performed by heating at a second temperature selected from a temperature range of 500 to 800 in a nitrogen atmosphere or an inert gas atmosphere for 4 to 8 hours.
  • Any heating means such as an electric furnace can be used for heating.
  • the polymerized nitriding source is carbonized by the carbon source (that is, the nitrogen atom and the carbon atom are bonded by a double bond or a double bond).
  • the reaction product obtained in the pores of the porous silica material is a carbon nitride porous material (MCN).
  • MCN carbon nitride porous material
  • the polymer obtained by polymerization may be dried to form fine particles. Thereby, the carbonization time can be shortened.
  • Step S 1 30 The obtained reaction product is removed from the porous silica material. By filtering the porous silica using hydrofluoric acid or alkaline aqueous solution, only the reactant MCN can be extracted. An arbitrary aqueous solution capable of dissolving the porous silica can be used. After step S 1 30, the extracted reactant may be washed and dried. For cleaning, pure water, distilled water, or ethanol is used.
  • FIG. 2 is a schematic view of a carbon nitride porous body (MCN) according to the present invention.
  • the carbon nitride porous body (MCN) 200 is an example when S B A- 15 is used as the porous silica body in the method described with reference to FIG.
  • the MCN 200 includes a pillar portion (indicated by a cylindrical bar piece in FIG. 2) and a bridge portion (indicated by a cylindrical small piece in FIG. 2) made of carbon nitride. It should be understood that the structure of MCN 200 depends on the selected silica porous material.
  • the pillars are regularly arranged in a hexagonal shape when S B A— 15 is used.
  • the bridges are much smaller than the pillars and connect the pillars together. Both the column part and the bridge part are made of carbon nitride.
  • the pore diameter is intended to be the distance between the pillars.
  • the pore size of MC N 200 according to the present invention is 4: 1111 to 1 01111. Since such a pore diameter corresponds to the diameter of various biological substances such as proteins, these biological substances can be immobilized in the MCN 200 pores.
  • the specific surface area of MCN 200 is more than 500 m 2 Zg, which can be advantageous for large-scale and delicate adsorption of external substances and substance sensing based thereon.
  • the ratio (C / N) of carbon atom (C) to nitrogen atom (N) in MCN 20 0 is CZN ⁇ 0.25, preferably 0.225 ⁇ CZN ⁇ 3.0.
  • MCN 200 obtained by the production method according to the present invention can increase the amount of nitrogen as compared with the conventional method, and thus has a large number of basic adsorption sites. As a result, excellent adsorptivity can be expected.
  • the carbon nitride porous body having the chemical formula C 3 N 4 it can be used as a semiconductor or high-strength material, which is the original property of carbon nitride, as a substitute for semiconductor devices or industrial diamond.
  • the reaction product thus obtained was subjected to structural analysis using an X-ray diffractometer (Siemens D5005, Brucker AX S, UK).
  • the operating conditions of the X-ray diffraction apparatus were 40 kV / 50 mA, scanning speed of 0.5 ° 20 minutes using Cu— ⁇ rays.
  • the X-ray diffraction pattern of MCN was compared with the X-ray diffraction pattern of the porous silica (SBA-1 5 in Example 1).
  • the reactants were observed using a high-resolution transmission electron microscope (J EOL-3100 F and JEOL-3100 FEF, JEOL, Japan).
  • the obtained reaction product was made into particles using a mortar and dispersed on a holey carbon film located on a grid made of Cu to prepare a sample.
  • the operating conditions of the transmission electron microscope were an acceleration voltage of 300 kV and a resolution of 150,000 to 120,000 times.
  • energy loss spectroscopy was performed using these high-resolution transmission electron microscopes.
  • elemental matbing was also performed at a resolution of 5 A using a standard 3-window procedure with a slit width of 20 eV.
  • the analysis region where energy loss and element mapping were performed was a region with a diameter of 100 to 200 nm.
  • Nitrogen adsorption / desorption isotherms were measured using a specific surface area / pore distribution measuring device (Au tosorb 1, Quantachrom, USA). Samples were measured at the 5 2 3 K at pressure 1 0- 5 h P a following 3 hours degassed after 7 7 K. By measuring the adsorption / desorption isotherm, the presence or absence of pores and the shape and size of the pores can be determined. The pore structure was analyzed using the B arrett-Jayner-Halenda method. Here, the MCN complex before removing SBA-15 (ie, the state where MCN is located in SBA-15) is used as a sample.
  • SBA-15 the state where MCN is located in SBA-15
  • the adsorption / desorption isotherm of the MCN complex was compared with the adsorption / desorption isotherm of SBA-15.
  • Infrared absorption spectra were measured using a Fourier transform infrared spectrophotometer (Nicolet Nexus 6700, Thermo Electron, USA). The measurement wavelength region was from 400 cm- 1 to 9500 cm- 1 .
  • X-ray photoelectron spectroscopic analysis was performed using an X-ray photoelectron spectrometer (E s c a la ab 20 00, VG Sci entif i c, UK). The analysis area was about 30 m in diameter. The above results are shown in FIGS. 3 to 9 and described in detail.
  • FIG. 3 is an X-ray diffraction pattern of MCN (a) and SBA-15 (b) obtained in Example 1.
  • the MCN X-ray diffraction pattern (a) was not due to the diffraction of the remaining SBA-15 itself.
  • the MCN showed a single broad diffraction peak at 25.8 °.
  • the interlayer distance d of MCN was found to be 3.42A. This value almost coincided with the interlayer distance d obtained with the non-porous carbon nitride sphere.
  • MCN is composed of dalaphen layers with carbon and nitrogen atoms arranged in an evening-bostratic (turbulent) form. From the above, it was shown that the obtained MCN reflects the periodically arranged pore structure of SBA_15.
  • FIG. 4 shows electron micrographs (a) and (b) and element mappings (c) and (d) of the MCN obtained in Example 1.
  • Fig. 4 (a) is a photograph observed from the [1 0 0] direction of MCN, and a striped pattern was confirmed.
  • Fig. 4 (a) bright stripes indicate pore walls and dark stripes indicate pores.
  • the inset in Fig. 4 (a) is a Fourier-transform light diffraction pattern obtained from the image, and shows a one-dimensional array of spots along the [1 0 0] direction. This indicates that there are no crystals arranged along the axis of the empty channel.
  • Figure 4 (b) is a cross-sectional view of the MCN (ie, a photograph observed from the direction perpendicular to the [1 0 0] direction). From Fig. 4 (b), it can be seen that the MCN porous bodies are arranged in the form of hexagonal crystals (ie, honeycomb). The inset in Fig. 4 (b) is the Fourier transform light diffraction pattern. From these, it can be seen that this is a hexagonal arrangement peculiar to the space group p 6 mm.
  • Figures 4 (c) and 4 (d) show the elemental mapping of carbon (C) and nitrogen (N), respectively. Other elements were not detected.
  • FIG. 5 is a diagram showing an electron energy loss spectrum of MCN obtained in Example 1.
  • the spectrum showed peaks at 2 84 eV and 40 1 eV. This These peaks suggest that there are carbon atoms (C k edge: absorption by carbon k-shell electrons) and nitrogen atoms (Nk edge: absorption by nitrogen k-shell electrons), respectively. Also, since the C k edge has a sharp peak shape, this indicates that the carbon k-shell electron (1 S electron) is excited into the empty antibonding 7 ⁇ electron orbit (ie, , I s—electronic transition).
  • FIG. 6 is a graph showing nitrogen adsorption / desorption isotherms of the MCN complex (a) and SBA-15 (b) obtained in Example 1.
  • the amount of nitrogen adsorbed by the MCN complex (a) decreased compared to the amount of nitrogen adsorbed by SBA-15 (b). This decrease corresponds to the deposited MCN.
  • Hysteresis was confirmed in the isotherms of (a) and (b).
  • the isotherm with such a shape was found to be type VI according to the IUP AC classification. That is, it suggests that mesopores (2-50 nm pores) exist in the MCN complex.
  • the nitrogen adsorption due to capillary condensation observed at relative pressures of 0.65 to 0.8 in SBA-15 (b) is shifted to a lower relative pressure in MCN complex (a).
  • FIG. 7 is a graph showing the pore size distribution of the MCN composite (a) and SBA-15 (b) obtained in Example 1.
  • the pore size distributions of MCN and SBA-15 were determined.
  • the pore diameter was determined from the pore volume distribution seen in the hysteresis of isotherms (a) and (b).
  • MCN was found to have a center of pore size distribution at 4.2 nm.
  • SBA-15 was found to have a pore size distribution stop at 7.1 nm. This indicates that the pore diameter of MCN is 1.2 nm larger than the wall thickness (3 nm) of SBA-15. This difference in pore diameter is due to the shrinkage of SBA-15 when the carbon nitride polymer filled in the pores of SBA-15 is treated at high temperature. Is caused by. Further, such a pore diameter can be changed according to the selected porous silica. Since the obtained pore size is similar to the size of high molecular weight biological molecules such as enzymes, it can be advantageous for selective immobilization of these substances.
  • 2 e V is due to the sp 2 hybrid orbital carbon atom bonded to the nitrogen atom in the aromatic structure.
  • the peak corresponding to 2 8 6. 8 e V is due to the sp 3 hybrid orbital, and the peak corresponding to 2 8 8. 7 e V is the highest energy in the aromatic ring bonded to the NH 2 group. due to carbon atoms in sp 2 hybrid orbitals.
  • the spectrum (c) indicating N ls in the spectrum (a) was divided into two peaks with binding energies of 39.78 eV and 400.2 eV.
  • the peak corresponding to 4 0. 2 e V is due to the nitrogen atom bonded to three carbon atoms in the amorphous C _N matrix.
  • Example 3 The same treatment as in Example 1 was carried out except that 2.81 g of ethylenediamine was used as the nitrogen source and 4.43 g of carbon tetrachloride was used as the carbon source. Table 1 shows the CZN ratio of the obtained MCN.
  • Example 3 The same treatment as in Example 1 was carried out except that 2.81 g of ethylenediamine was used as the nitrogen source and 4.43 g of carbon tetrachloride was used as the carbon source. Table 1 shows the CZN ratio of the obtained MCN.
  • Example 3 Example 3;
  • Example 4 The same treatment as in Example 1 was performed, except that 2.35 g of ethylenediamine was used as the nitrogen source and 2.36 g of carbon tetrachloride was used as the carbon source. Table 1 shows the CZN ratio of the obtained MCN.
  • Example 4 The same treatment as in Example 1 was performed, except that 2.35 g of ethylenediamine was used as the nitrogen source and 2.36 g of carbon tetrachloride was used as the carbon source. Table 1 shows the CZN ratio of the obtained MCN.
  • Example 4 The same treatment as in Example 1 was performed, except that 2.35 g of ethylenediamine was used as the nitrogen source and 2.36 g of carbon tetrachloride was used as the carbon source. Table 1 shows the CZN ratio of the obtained MCN.
  • Example 4 The same treatment as in Example 1 was performed, except that 2.35 g of ethylenediamine was used as the nitrogen source and 2.36 g of carbon tetrachloride was used as the carbon source. Table 1
  • Example 5 The same treatment as in Example 1 was carried out except that 3.48 g of ethylenediamine was used as the nitrogen source and 0.31 g of carbon tetrachloride was used as the carbon source. Table 1 shows the CZN ratio of the obtained MCN.
  • Example 5 The same treatment as in Example 1 was carried out except that 3.48 g of ethylenediamine was used as the nitrogen source and 0.31 g of carbon tetrachloride was used as the carbon source. Table 1 shows the CZN ratio of the obtained MCN.
  • Example 5 The same treatment as in Example 1 was carried out except that 3.48 g of ethylenediamine was used as the nitrogen source and 0.31 g of carbon tetrachloride was used as the carbon source. Table 1 shows the CZN ratio of the obtained MCN.
  • Example 5 The same treatment as in Example 1 was carried out except that 3.48 g of ethylenediamine was used as the nitrogen source and 0.31 g of carbon tetrachloride was used as the carbon source. Table 1
  • Example 6 The same treatment as in Example 1 was performed, except that 2.50 g of hydrazine was used as the nitrogen source and 3.33 g of carbon tetrachloride was used as the carbon source. Table 1 shows the CZN ratio of the obtained MCN.
  • Example 6 The same treatment as in Example 1 was performed, except that 2.50 g of hydrazine was used as the nitrogen source and 3.33 g of carbon tetrachloride was used as the carbon source. Table 1 shows the CZN ratio of the obtained MCN.
  • Example 6 The same treatment as in Example 1 was performed, except that 2.50 g of hydrazine was used as the nitrogen source and 3.33 g of carbon tetrachloride was used as the carbon source. Table 1 shows the CZN ratio of the obtained MCN.
  • Example 6 The same treatment as in Example 1 was performed, except that 2.50 g of hydrazine was used as the nitrogen source and 3.33 g of carbon tetrachloride was used as the carbon source. Table 1
  • Example 1 The same treatment as in Example 1 was performed, except that 3.50 g of hydrazine was used as the nitrogen source and 0.48 g of carbon tetrachloride was used as the carbon source. Table 1 shows the CZN ratio of the obtained MCN. table 1 :
  • the carbon nitride porous body obtained in this way has an adsorptivity that surpasses the properties of the conventional porous body, and thus can replace the conventional porous body.
  • the carbon nitride porous body produced by the method according to the present invention is applicable to an adsorbent, a separating agent, a single catalyst, a battery electrode, a capacitor, and an energy storage body.
  • a carbon nitride porous body represented by the chemical formula C 3 N 4 having a hardness equal to or higher than that of diamond can be produced. This makes it possible to replace conventional industrial diamonds. Further, it may be used for a semiconductor device or a light emitting device utilizing the property of carbon nitride semiconductor.
  • the pore structure is suitable for immobilization of biological materials, it can be applied to bioreactors with excellent mechanical strength and high durability, and various biosensors based on semiconducting properties.

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Abstract

L'invention concerne un procédé qui permet la préparation d'une matière en nitrure de carbone poreux ayant une teneur en azote souhaitée avec facilité et qui peut également régler une valeur C/N précisément sur une large plage. Ledit procédé servant à préparer une matière en nitrure de carbone poreux (MCN) comprend une étape consistant à mélanger une matière en silice poreuse, une source d'azote et une source de carbone, une étape consistant à chauffer le mélange obtenu dans l'étape de mélange et une étape consistant à enlever la matière en silice poreuse du produit de réaction obtenu dans l'étape de chauffage, l'étape de chauffage comprenant une étape consistant à convertir le mélange en une matière polymérique à une première température et une étape consistant à carboniser le mélange à une seconde température laquelle est supérieure à la première température.
PCT/JP2005/020149 2004-10-29 2005-10-27 Matière en nitrure de carbone poreux et procédé pour la préparation de celle-ci WO2006046756A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010030844A (ja) * 2008-07-30 2010-02-12 National Institute For Materials Science 窒化炭素多孔体（ｍｃｎ）を製造する方法
CN104607231A (zh) * 2015-02-16 2015-05-13 江苏理工学院 具有三维有序大孔结构的氮化碳光催化剂及其制备方法
WO2018037322A1 (fr) * 2016-08-22 2018-03-01 Sabic Global Technologies B.V. Matériaux de nitrure de carbone mésoporeux en forme de tige et leurs utilisations
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