WO2010077011A2 - Procédé de production d'une nanofibre de carbone composite ayant une activité photocatalytique, nanofibre de carbone composite ayant une activité photocatalytique produite au moyen du procédé, filtre comprenant la nanofibre de carbone composite et sol de photocatalyseur thermiquement stable employé dans le procédé de production - Google Patents

Procédé de production d'une nanofibre de carbone composite ayant une activité photocatalytique, nanofibre de carbone composite ayant une activité photocatalytique produite au moyen du procédé, filtre comprenant la nanofibre de carbone composite et sol de photocatalyseur thermiquement stable employé dans le procédé de production Download PDF

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WO2010077011A2
WO2010077011A2 PCT/KR2009/007733 KR2009007733W WO2010077011A2 WO 2010077011 A2 WO2010077011 A2 WO 2010077011A2 KR 2009007733 W KR2009007733 W KR 2009007733W WO 2010077011 A2 WO2010077011 A2 WO 2010077011A2
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carbon nanofiber
composite carbon
photocatalytic activity
sol solution
photocatalyst
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PCT/KR2009/007733
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English (en)
Korean (ko)
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WO2010077011A3 (fr
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양갑승
김보혜
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전남대학교산학협력단
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Publication of WO2010077011A3 publication Critical patent/WO2010077011A3/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts

Definitions

  • the present invention relates to carbon nanofibers, and more specifically, to a method for producing a composite carbon nanofiber having a photocatalytic activity, a composite carbon nanofiber prepared by the manufacturing method thereof, a filter including the composite carbon nanofiber, and the composite carbon nanofiber.
  • sources of environmental pollution present in water can be largely classified into suspended matter, dissolved organic matter and dissolved inorganic matter.
  • the suspended solids with a high specific gravity among the suspended solids can be removed by sedimentation method.
  • suspended solids which are relatively hard to settle they can be removed by floating flotation using saturated air bubbles.
  • advances in industrialization have resulted in the release of large quantities of biologically degradable substances that are difficult for microorganisms to degrade. These hardly decomposable materials are rarely removed by the conventional activated sludge process using mixed suspended microorganisms, causing serious environmental pollution.
  • Photocatalysts are "materials that do not change themselves when irradiated with light, but catalyze chemical reactions.” It refers to a substance that advances the catalytic reaction using light as an energy source, and a semiconductor metal oxide or a sulfur compound is used as the photocatalyst. Such photocatalysts have been known to decompose various biologically hardly decomposable substances that existing microorganisms cannot remove. Examples of such photocatalysts include ZnO, WO 3 , SnO 2 , ZrO 2 , TiO 2 , and CdS. There is this.
  • titanium dioxide (TiO 2 ) having an anatase crystal structure is particularly used.
  • the energy required to cause the photoexcitation reaction is 387.5 nm, and sufficient energy can be received from sunlight. This is because it is excellent in physical properties such as harmless to the human body.
  • radicals have high oxidation and reduction potentials, they are excellent for NO x , SO x , volatile organic compounds (VOCs) and various odor purification, BOD, color and hardly degradable contaminants of livestock wastewater, sewage, factory wastewater, environment In addition to removing hormones, it can sterilize over 99% of pathogens and bacteria such as Escherichia coli, Staphylococcus aureus, and O-157.
  • titanium dioxide powder having anatase crystal structure has excellent photocatalytic properties and is relatively easy to synthesize, and many studies on this have been conducted (US Pat. No. 6,022,824).
  • titanium dioxide powder has a problem that the size of the titanium dioxide powder is about 0.1 ⁇ m or less, which is very small, so that a membrane such as a membrane may be used to recover the titanium dioxide powder when it is manufactured with a continuous flow type water treatment reactor (US Pat. No. 5,462,674).
  • the titanium dioxide powder accumulates on the separation membrane surface, resulting in shortening the life of the membrane, and consequently has a problem of lowering the removal efficiency of the entire water treatment reactor system.
  • US Patent Nos. 5,591,380, 4,176,089 and the like have a problem in that when the two types of sol are uniformly dispersed in the support, the stability of the sol is lowered and is easily gelled to thicken the coating film or the process is complex.
  • Korean Patent Laid-Open Publication Nos. 2001-0084574 and 10-2004-0003759 propose a method for producing a titanium dioxide photocatalyst supported or supported on silica gel.
  • it was used after calcining heat treatment at 400 ⁇ 600 °C.
  • These photocatalysts are phase-changed into a rutile structure at a high temperature, and the efficiency of the photocatalyst is drastically reduced.
  • carbon nanofibers are a new type of activated carbon having a nanographite structure, which is a new type of carbon material capable of mass production, having a large specific surface area and excellent conductivity.
  • activated carbon which is a kind of adsorbent
  • carbon nanofibers have a large specific surface area, shallow depth of pores, and micropores of 1-2 nm size. It can be used for effective adsorption, decolorization, water treatment agent, deodorant, moisture absorbent and the like.
  • carbon nanofibers use only the adsorptivity of the porous structure, and when the adsorption is completed, the purification ability is sharply reduced.
  • the present inventors have a photocatalytic property using carbon nanofibers and a photocatalyst material and at the same time have the inherent properties of carbon nanofibers, and a composite carbon nanofiber manufacturing method having a photocatalytic activity having a superior purification function and a composite carbon manufactured by the method Nanofibers were developed to complete the present invention.
  • an object of the present invention is a method for producing a composite carbon nanofiber having a photocatalytic activity of simultaneously adsorbing and decomposing organic substances by simultaneously retaining the inherent adsorption capacity of carbon nanofibers and the decomposition ability of the photocatalyst, and composite carbon nanoparticles prepared by the method It is to provide a filter comprising a fiber and the composite carbon nanofibers.
  • Another object of the present invention is a composite carbon nanofiber manufacturing method having a photocatalytic activity which shows a high photoactivity compared to the existing photocatalyst, and has a high photocatalytic activity in the chromaticity treatment of high concentration dyeing waste water due to excellent photolysis ability of high concentration dye, It is to provide a filter comprising a composite carbon nanofibers and the composite carbon nanofibers prepared by.
  • Still another object of the present invention is a method for producing a composite carbon nanofiber having a photocatalytic activity having a photocatalytic activity of adsorbing and decomposing harmful gases as well as photocatalytic reaction of a general organic compound even at a high temperature, and a composite carbon nanofiber prepared by the method. It is to provide a filter comprising a composite carbon nanofibers.
  • Still another object of the present invention is a composite carbon nanofiber manufacturing method having a photocatalytic activity which is extremely suitable to be widely used in air purifier filters, automobile exhaust gas purification filters, water purification filters, composite carbon nanofibers prepared by the method It is to provide a filter comprising the composite carbon nanofibers.
  • the present invention comprises the steps of stabilizing the carbon nanofiber precursor obtained by electrospinning the spinning solution in which the carbon fiber precursor material is dissolved at 200 to 350 °C to obtain a flame-resistant fiber; Preparing a photocatalyst sol solution; Coating the chlorinated fiber by dipping the photocatalyst sol solution; And it provides a composite carbon nanofiber manufacturing method having a photocatalytic activity comprising the step of carbonizing the coated flame resistant fiber after drying.
  • the photocatalyst is any one selected from the group of ZnO, WO 3 , SnO 2 , ZrO 2 , TiO 2 , CdS.
  • SiO 2 is further added to prepare a photocatalyst sol solution.
  • the photocatalyst sol solution to which SiO 2 is further added is obtained by preparing a SiO 2 sol solution and then stirring while adding the photocatalyst.
  • the carbonization step is carried out by heating to 900 ° C.
  • the carbon nanofiber precursor material is any one selected from the group consisting of polyacrylo nitrile (PAN), polyimide, polybenzimidazole (PBI), and pitch. .
  • the present invention provides a carbon nanofiber having a photocatalytic activity prepared by the method of any one of claims 1 to 6, wherein the included photocatalyst is titanium dioxide, the composite carbon nanofibers having a photocatalytic activity. do.
  • the crystal structure of the titanium dioxide has anatase structure of 50% or more.
  • the specific surface area of the composite carbon nanofibers having the photocatalytic activity is 254 m 2 / g.
  • the present invention also provides a filter having a stable photocatalytic activity even at high temperature, including the composite carbon nanofibers having the photocatalytic activity of claim 7.
  • the present invention is a photocatalyst that is coated on the surface of the material to give the photocatalytic activity is further included in a state in which SiO 2 is dispersed in a sol solution in which titanium dioxide is dispersed is more than 750 °C in titanium dioxide coated on the surface of the material
  • a thermally stable photocatalyst sol solution characterized in that the crystal structure of the titanium dioxide is inhibited from phase transition from anatase to rutile crystal structure even when heat is applied.
  • the thermally stable photocatalyst sol solution is tetraethyl orthosilicate (TEOS), titanium isopropoxide (TiP), ethanol (Ethyl alcohol) having a purity of 98% or more. ), Water and 0.05 N HCl, the TEOS and TiP is in a dispersed state.
  • the thermally stable photocatalyst sol solution is obtained by mixing TEOS, water, and 0.05 N HCl in the ethanol to prepare a silica sol solution, followed by stirring while adding TiP.
  • the present invention has the following excellent effects.
  • the composite carbon nanofibers prepared by the method of manufacturing the composite carbon nanofiber of the present invention and the filter including the composite carbon nanofibers have the adsorption capacity and the photocatalytic decomposition ability of carbon nanofibers at the same time to decompose organic substances simultaneously with adsorption. It has excellent photocatalytic activity.
  • the composite carbon nanofibers produced by the composite carbon nanofiber manufacturing method of the present invention and the filter including the composite carbon nanofibers show higher photoactivity than conventional photocatalysts, and have excellent photodegradation ability of high-density dyes for color treatment of highly concentrated dye wastewater. High purification efficiency can be obtained.
  • the composite carbon nanofibers prepared by the composite carbon nanofiber manufacturing method of the present invention and the filter including the composite carbon nanofibers have excellent photocatalytic activity having the adsorption and decomposition function of harmful gases as well as photodegradation reaction of general organic compounds even at high temperature.
  • the composite carbon nanofibers produced by the composite carbon nanofiber manufacturing method of the present invention and the filter including the composite carbon nanofibers are excellent photocatalysts that are extremely suitable for being widely used in air purifier filters, automobile exhaust gas purification filters, and water purification filters. Have activity.
  • the thermally stable photocatalyst sol solution that can be used in the composite carbon nanofiber manufacturing method of the present invention is an anatase structure in which the crystal structure of titanium dioxide has thermal stability even when heat of 750 ° C. or more is applied to titanium dioxide used as a photocatalyst to impart photocatalytic activity. It has a composition to maintain the high light activity.
  • FIG. 1 is a flow chart briefly showing each process of the composite carbon nanofiber manufacturing method having a photocatalytic activity according to an embodiment of the present invention
  • FIG. 2 is an electron micrograph of a composite carbon nanofiber coated with a photocatalyst by the method of FIG. 1
  • FIG. 3 is a graph of an energy dispersive X-ray spectrometer (EDX)
  • XRD 4 is a graph of X-ray diffraction analysis (XRD) of TiO 2 / SiO 2 coated composite carbon nanofibers
  • XRD 5 is a graph of X-ray diffraction analysis (XRD) of TiO 2 coated carbon nanofibers
  • the composite carbon nanofiber manufacturing method having the photocatalytic activity of the present invention does not coat the photocatalyst on the finished product as is generally known, but rather the photocatalyst is coated in the carbon nanofiber manufacturing process, that is, the photocatalyst is immersed in the flame resistant fiber. After the carbonization process to warm up to 900 °C to finally produce a composite carbon nanofibers having a photocatalytic activity.
  • the photocatalyst constitutes a part of the carbon nanofibers, so that the photocatalyst naturally forms a fixed phase and the organic catalyst to which the photocatalyst can act can be easily adsorbed by the adsorption capacity of the carbon nanofibers.
  • the activity can be significantly improved, making it extremely suitable for use as a filter.
  • the composite carbon nanofiber manufacturing method of the present invention further provides a technical configuration that can lower or maintain or improve the degree of degradation of the photocatalytic activity even at a carbonization process of 900 ° C. when the photocatalyst used is not thermally stable. It is preferable.
  • titanium dioxide which is most commonly used as a general photocatalyst, has two crystal structures, rutile and anatase. Due to the structural difference between the crystals, anatase (3.2 eV) It has a bandgap slightly larger than rutile (3.0 eV), which results in fast electron-hole recombination reactions on the rutile surface, with fewer rutiles than anatase in the number of reactants attached to the surface and the amount of hydroxyl groups on the surface Because of this, the light efficiency of anatase is generally higher than rutile, so it is desirable to have an anatase structure even at high temperatures.
  • Titanium dioxide begins to phase change its crystal structure from anatase to rutile crystal structure at 750 ° C, and at the firing temperature above 900 ° C, no meta-stable anatase peak is observed in the X-ray diffractometer (XRD). Only in rutile peaks are measured.
  • the present invention provides a thermally stable photocatalyst sol solution that can be used in a method for producing a composite carbon nanofiber having a photocatalytic activity, that is, to maintain the photocatalytic activity of titanium dioxide even at a temperature of more than 900 °C.
  • FIG. 1 is a flow chart briefly showing each process of the composite carbon nanofiber manufacturing method having a photocatalytic activity according to an embodiment of the present invention
  • Figure 2 is a photocatalyst coated electron of the composite carbon nanofibers by the method of Figure 1
  • 3 is a graph of an energy dispersive X-ray spectrometer (EDX)
  • FIG. 4 is a graph of X-ray diffraction analysis (XRD) of TiO 2 / SiO 2 coated carbon nanofibers
  • FIG. 5 is TiO 2 a graph of X-ray diffraction analysis (XRD) of the coated carbon nano-fiber
  • Fig. 6 is a TiO 2 / SiO 2 coating of carbon and FT-IR graph of a nano fiber
  • TiO 2 / SiO 2 coating the composite carbon nano The concentration of Methylene blue solution was determined by irradiating UV rays to fibers [(TiO 2 / SiO 2 ) / CNFs], TiO 2 coated carbon nanofibers [TiO 2 / CNFs] and composite carbon nanofibers [CNFs]. This is a graph analyzed by VU-Vis spectrophotometer.
  • the composite carbon nanofibers having the photocatalytic activity were prepared by performing the process shown in FIG. 1 as follows.
  • PAN for carbon fiber was dissolved in dimethyformamide (DMF) to prepare a spinning solution.
  • This PAN solution was prepared using a non-woven web composed of nanofibers using an electrospinning method.
  • the electrospinning apparatus applied an applied voltage of 30 kV to the nozzle and the collector, respectively, and the distance between the spinneret and the collector was varied as needed about 10 to 30 cm.
  • the PAN spinning fiber obtained by electrospinning was supplied with compressed air at a flow rate of 5-20 mL per minute using a hot air circulating fan, and stabilized by maintaining it at 200-300 ° C. for 1 hour at a temperature rising rate of 1 ° C. per minute. Got.
  • the TiO 2 / SiO 2 sol solution a thermally stable photocatalyst sol solution, contains tetraethyl orthosilicate (TEOS), Titanium (IV) isopropoxide TiP, Ethanol (Ethyl alcohol) was purchased and used as it is.
  • TEOS tetraethyl orthosilicate
  • IV Titanium
  • Ethanol Ethyl alcohol
  • PAN flame-resistant fiber was immersed in TiO 2 / SiO 2 sol solution for 2 hours, dried in air, and carbonized by heating to 900 ° C. at a heating rate of 5 ° C. per minute (ie, TiO 2 / SiO 2 coated carbon nanofibers) was prepared.
  • TiO 2 -coated composite carbon nanofibers were prepared in the same manner as in Example.
  • FIG. 2 In order to confirm the presence of the photocatalyst in the composite carbon nanofibers having the photocatalytic activity prepared in Example 1, it is shown in FIG. 2 by an electron microscope, and a graph of an energy dispersive X-ray spectrometer (EDX) is shown in FIG. 3. .
  • EDX energy dispersive X-ray spectrometer
  • TiO 2 which is an ultrafine photocatalyst particle having a size of 20-40 nm, was uniformly distributed on the surface of the carbon nanofibers.
  • FIG. 3 is a graph of an energy dispersive X-ray spectrometer (EDX).
  • Example 1 TiO 2 / SiO 2 composite coating of carbon nanofiber as in Example 2 X- ray diffraction whether maintaining the photocatalytic TiO 2 the photocatalytic activity include the production of TiO 2 coated with the composite manufactured from the carbon nanofiber The pattern was examined and the results are shown in Table 1, FIG. 4 and FIG. 5.
  • Ti-O-Si shows a specific peak of Ti-O-Si at 930 cm -1 , which shows that silica (SiO 2 ) is dispersed in TiO 2 to prevent phase transition to rutile crystals, thereby maintaining the structure of anatase.
  • SiO 2 prevents TiO 2 from agglomerating at high temperature by disturbing the movement of TiO 2 particles and molecules, thereby increasing the particle size and inhibiting phase transition from anatase to rutile.
  • a solution of methylene blue (MB) dye was prepared at a concentration of 10 ppm. 100 mL of this solution and 0.1 g of TiO 2 / SiO 2 coated carbon nanofibers or TiO 2 coated carbon nanofibers were placed in a beaker and irradiated with UV (8 W, 365 nm, Sankyo Denki) to observe dye degradation performance. It was. After the reaction, 3 mL of the reaction solution was collected at regular time intervals to confirm the change in concentration of MB, and the solution was separated using a 0.45 ⁇ m (Millipore millex filter) filtration membrane to obtain a pure solution containing no TiO 2 particles. . The concentration of MB according to reaction time was measured by UV-Vis spectroscopy.
  • TiO 2 was used as the photocatalyst, but similar results can be obtained using other photocatalyst materials ZnO, WO 3 , SnO 2 , ZrO 2 , and CdS. Do not exclude that.
  • any one selected from the group consisting of polyimide, polybenzimidazole (PBI), and pitch in addition to polyacrylo nitrile (PAN) may be used. have.
  • the crystal structure of titanium dioxide has anatase structure of 50% or more and the specific surface area. Since it is more than 254 m 2 / g, it has the function of adsorption and decomposition of harmful gases as well as photodegradation reaction of general organic compounds even at high temperature. Therefore, the filter including the composite carbon nanofibers may be widely used in air purifier filters, automobile exhaust gas reduction filters, and the like, and may be widely used as water purification filters because it may decompose wastewater treatment, pollutants and pigments in water. Can be.
  • the thermally stable photocatalyst sol solution of the present invention is capable of maintaining the crystal structure of the titanium dioxide in the anatase structure even when heat of 750 ° C. or more is applied to the titanium dioxide dispersed in the solution, thereby providing a composite carbon nanofiber having the photocatalytic activity of the present invention.
  • it can be variously applied to the field to have a photocatalytic activity at a high temperature using another material.

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Abstract

La présente invention concerne une nanofibre de carbone et plus particulièrement un procédé pour produire une nanofibre de carbone composite ayant une activité photocatalytique, une nanofibre de carbone composite produite au moyen du procédé, un filtre comprenant la nanofibre de carbone composite et un sol de photocatalyseur thermiquement stable employé pour la production de la nanofibre de carbone composite.
PCT/KR2009/007733 2008-12-31 2009-12-23 Procédé de production d'une nanofibre de carbone composite ayant une activité photocatalytique, nanofibre de carbone composite ayant une activité photocatalytique produite au moyen du procédé, filtre comprenant la nanofibre de carbone composite et sol de photocatalyseur thermiquement stable employé dans le procédé de production WO2010077011A2 (fr)

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KR10-2008-0137971 2008-12-31
KR20080137971A KR101083060B1 (ko) 2008-12-31 2008-12-31 광촉매활성을 갖는 복합탄소나노섬유 제조방법, 그 방법으로 제조된 광촉매활성을 갖는 복합탄소나노섬유, 상기 복합탄소나노섬유를 포함하는 필터 및 상기 제조방법에 사용되는 열 안정성 광촉매 졸 용액

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CN105126886A (zh) * 2015-07-01 2015-12-09 宁波工程学院 一种TiO2/WO3/g-C3N4全介孔纳米纤维的制备方法
CN105126892A (zh) * 2015-07-01 2015-12-09 宁波工程学院 一种TiO2/WO3/g-C3N4全介孔纳米纤维在高效光催化剂中的应用
CN105148965A (zh) * 2015-07-01 2015-12-16 宁波工程学院 一种TiO2/WO3/g-C3N4全介孔纳米纤维
CN110756228A (zh) * 2019-11-19 2020-02-07 北京工业大学 一种多级结构TiO2/C@MOF纳米纤维膜光催化材料的制备方法和应用
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CN112813531A (zh) * 2021-01-04 2021-05-18 周菊青 一种二氧化钛纳米花改性聚丙烯腈纳米纤维脱硫剂及制法
CN113351174A (zh) * 2021-06-18 2021-09-07 东北电力大学 一种负载v/n掺杂纳米二氧化钛的hkust-1/cnf复合膜的制备方法及应用

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KR101270716B1 (ko) * 2011-08-26 2013-06-03 전남대학교산학협력단 광촉매-그래핀-탄소나노섬유복합체 제조방법
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