JP2019503325A - Flexible metal oxide nanofibers prepared by electrospinning, stable nanofiber fabrics produced thereby, and production methods - Google Patents
Flexible metal oxide nanofibers prepared by electrospinning, stable nanofiber fabrics produced thereby, and production methods Download PDFInfo
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- JP2019503325A JP2019503325A JP2018534601A JP2018534601A JP2019503325A JP 2019503325 A JP2019503325 A JP 2019503325A JP 2018534601 A JP2018534601 A JP 2018534601A JP 2018534601 A JP2018534601 A JP 2018534601A JP 2019503325 A JP2019503325 A JP 2019503325A
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- nanofibers
- stable
- nanofiber
- metal oxide
- flexible
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 260
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 59
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 238000001523 electrospinning Methods 0.000 title claims abstract description 12
- 239000004744 fabric Substances 0.000 title abstract 2
- 238000001354 calcination Methods 0.000 claims abstract description 65
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 25
- WOSCWBLSTPSYFY-UHFFFAOYSA-N oxotungsten zinc Chemical compound [W]=O.[Zn] WOSCWBLSTPSYFY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 15
- 239000002073 nanorod Substances 0.000 claims abstract description 15
- 239000002356 single layer Substances 0.000 claims abstract description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract 2
- 239000012528 membrane Substances 0.000 claims description 71
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052721 tungsten Inorganic materials 0.000 claims description 19
- 239000010937 tungsten Substances 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 17
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 239000004408 titanium dioxide Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- 229920001002 functional polymer Polymers 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
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- 150000004696 coordination complex Chemical class 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
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- 238000002256 photodeposition Methods 0.000 claims description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
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- 150000003751 zinc Chemical class 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 3
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
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- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000223 polyglycerol Polymers 0.000 claims description 2
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000001035 drying Methods 0.000 abstract 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 81
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 51
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 42
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 24
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- 238000000354 decomposition reaction Methods 0.000 description 14
- 238000011161 development Methods 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000007540 photo-reduction reaction Methods 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 7
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- 238000004458 analytical method Methods 0.000 description 4
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
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- QPFYXYFORQJZEC-UHFFFAOYSA-N phenazopyridine Chemical compound NC1=NC(N)=CC=C1N=NC1=CC=CC=C1 QPFYXYFORQJZEC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/62259—Fibres based on titanium oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
- B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
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Abstract
本発明は、安定で設計どおりの金属酸化物ナノ繊維及びそのナノ繊維から作成された可撓性で安定なナノ繊維布帛に関する。ナノ繊維の製造方法は、エレクトロスピニングでナノ繊維を製造してから、乾燥及び仮焼して金属酸化物を形成することを含む。ナノ繊維は主成分としてアナターゼ及びルチル型のチタン二酸化物及びタングステン酸化物からなる。ナノ繊維の表面は亜鉛タングステン酸化物（サンマルチナイト）ナノロッドを含む。さらに、ナノ繊維及び亜鉛タングステン酸化物ナノロッドの表面は単層の貴金属ナノ粒子によって修飾されている。光触媒物質は可視光、ＵＶ及び太陽光の下で作用し得る。ナノ寸法材料は微細孔と高い比表面積を有する。本発明はタングステン酸化物（ＷＯ３）ナノ繊維の脆さ及び不安定性の課題を解決できる。The present invention relates to stable and designed metal oxide nanofibers and flexible and stable nanofiber fabrics made from the nanofibers. The method for producing nanofibers includes producing nanofibers by electrospinning and then drying and calcining to form a metal oxide. Nanofibers are composed of anatase and rutile titanium dioxide and tungsten oxide as main components. The surface of the nanofiber includes zinc tungsten oxide (sun multinite) nanorods. Furthermore, the surfaces of the nanofibers and zinc tungsten oxide nanorods are modified with a single layer of noble metal nanoparticles. The photocatalytic material can work under visible light, UV and sunlight. Nano-dimensional materials have micropores and a high specific surface area. The present invention can solve the problems of brittleness and instability of tungsten oxide (WO3) nanofibers.
Description
化学は、可撓性、安定性及び製造可能性を有する金属酸化物ナノ繊維及びナノ繊維膜触媒に関する。 Chemistry relates to metal oxide nanofibers and nanofiber membrane catalysts having flexibility, stability and manufacturability.
揮発性有機化合物（ＶＯＣ）による環境の大気汚染物質は主に乗り物のエンジン燃焼によって発生しているので、ＶＯＣ削減の新しい技術開発が現在の状況における重要課題である。興味あるＶＯＣ削減技術の１つは、光を活性化エネルギー源として利用する光触媒である。一般的に、光触媒反応は、不特定の有機物分解に適した、有機分子の酸化還元反応に光を必要とする。 Since environmental air pollutants due to volatile organic compounds (VOC) are generated mainly by vehicle engine combustion, the development of new technology to reduce VOC is an important issue in the current situation. One interesting VOC reduction technique is a photocatalyst that utilizes light as an activation energy source. In general, photocatalytic reactions require light for redox reactions of organic molecules, which are suitable for unspecified organic matter decomposition.
光触媒反応は液相及び気相の両方で起きることが可能であるので、この技術は非常に多様性があり、広範囲の用途を有する。加えて、この技術の多くの利点は、例えば、自浄性、安価な材料、低い維持コストなど、産業規模の製造に高い可能性をもたらす。しかしながら、光触媒材料の殆どは、触媒が可視光では制御できない大きなバンドギャップを有しているので、主にＵＶ光にある高い活性化エネルギーを必要とする。したがって、この欠点がこの技術を産業規模で利用することを制限している。さらに、光触媒反応は主に触媒の表面で起きるので、触媒の形状及び寸法が有機物分解効率に重要な役割を示す。このため、ナノ光触媒が高い比表面積を有するので最も適当な材料であってよい。しかしながら、ナノ光触媒は凝集性と再循環効率の問題がある。他方、フィルム光触媒は容易に再循環可能であるが、限られた比表面積を有しているので有機物分解効率が低い。ナノ繊維は、高い比表面積、再循環性及び非凝集性の材料であり、ナノ粒子及びフィルム材料の両方に固有の不利を克服することが可能である。 Since photocatalytic reactions can occur in both liquid and gas phases, this technique is very diverse and has a wide range of applications. In addition, the many advantages of this technology offer high potential for industrial scale manufacturing, for example, self-cleaning, inexpensive materials, and low maintenance costs. However, most photocatalytic materials require high activation energy, mainly in UV light, because the catalyst has a large band gap that cannot be controlled with visible light. This drawback therefore limits the use of this technology on an industrial scale. Furthermore, since the photocatalytic reaction occurs mainly on the surface of the catalyst, the shape and size of the catalyst play an important role in the organic matter decomposition efficiency. For this reason, since a nanophotocatalyst has a high specific surface area, it may be the most suitable material. However, nanophotocatalysts have problems of agglomeration and recycling efficiency. On the other hand, the film photocatalyst can be easily recycled, but has a limited specific surface area, so that the organic matter decomposition efficiency is low. Nanofibers are high specific surface area, recyclable and non-agglomerated materials, and can overcome the disadvantages inherent in both nanoparticles and film materials.
有機汚染物分解のほかに、光触媒は応用分野を広げるために耐微生物性を有していなければならない。水汚染物分解では、液相で光触媒を用いる重要な欠陥の１つは回収プロセスにある。回収プロセスの１つは遠心分離法である。この方法は実験室規模では非常に効率的であるが、産業的製造及び応用では非常にコストがかかる。結論として、ナノ材料の応用はろ過プロセスに問題がある一方、フィルム材料は低比表面積に問題がある。他方、ナノ繊維の光触媒材料は再循環性及び高比表面積に関する両方の問題を克服することが可能である。 Besides decomposing organic pollutants, the photocatalyst must be resistant to microorganisms in order to expand its application field. In water contaminant decomposition, one of the important deficiencies of using photocatalysts in the liquid phase is in the recovery process. One recovery process is centrifugation. While this method is very efficient on a laboratory scale, it is very costly for industrial manufacturing and application. In conclusion, application of nanomaterials has problems with the filtration process, while film materials have problems with low specific surface area. On the other hand, nanofiber photocatalytic materials can overcome both the problems of recyclability and high specific surface area.
通常、ナノ粒子合成方法は、高温又は真空装置など、高いコストと非環境フレンドリーなプロセスが必要である。その結果、製造コストと消費時間が増加しえる。 Typically, nanoparticle synthesis methods require high cost and non-environment friendly processes such as high temperature or vacuum equipment. As a result, manufacturing costs and consumption time can increase.
廃水処理は触媒を主成分として用いる適当な方法が必要である。光触媒は、その触媒化学組成物が低コストであり、反応を触媒するのに自然の太陽光を利用できるので、最も期待される方法の１つである。しかしながら、光触媒は、触媒光が制限された領域であること、高い脆性の２つの主な欠点がある。 Waste water treatment requires an appropriate method using a catalyst as a main component. Photocatalysts are one of the most promising methods because their catalytic chemical composition is low cost and natural sunlight can be used to catalyze the reaction. However, the photocatalyst has two main drawbacks, that is, a region where the catalyst light is limited and high brittleness.
本発明は、貴金属で修飾された二酸化チタン及び亜鉛タングステン酸化物ナノ繊維及びナノ繊維膜の製造に関する。開示されるナノ繊維及びナノ繊維膜は、安定で、可撓性で、容易に製造可能であり、可視光、ＵＶ及び自然太陽光で作用可能である。本発明は、他の製造方法とは化学組成、金属酸化物ナノ繊維膜の安定性が異なる特定の組み合わせによって製造される。 The present invention relates to the production of titanium dioxide and zinc tungsten oxide nanofibers and nanofiber membranes modified with noble metals. The disclosed nanofibers and nanofiber membranes are stable, flexible, easily manufacturable and can operate in visible light, UV and natural sunlight. The present invention is manufactured by a specific combination in which the chemical composition and the stability of the metal oxide nanofiber film are different from other manufacturing methods.
文献及び特許検索によれば、以下に示すように、本発明と類似するものは見つからなかった。 According to the literature and patent search, as shown below, nothing similar to the present invention was found.
非特許文献１：“Enhanced photocatalytic activity of palladium decorated TiO2 nanofibers containing anatase-rutile mixed phase”：この文献は、オートクレーブ及び仮焼によるパラジウム修飾された二酸化チタンナノ繊維の製造に関する。成果は、水素化及び有機染料分解反応用の触媒である。これは、金属酸化物材料の組成が本発明とは異なる。加えて、この文献は金属酸化物ナノ繊維膜の安定性の開発について記載がない。 Non-Patent Document 1: “Enhanced photocatalytic activity of palladium decorated TiO 2 nanofibers containing anatase-rutile mixed phase”: This document relates to the production of palladium-modified titanium dioxide nanofibers by autoclaving and calcination. The result is a catalyst for hydrogenation and organic dye decomposition reactions. This differs from the present invention in the composition of the metal oxide material. In addition, this document does not describe the development of the stability of metal oxide nanofiber membranes.
非特許文献２：“ZnWO4 photocatalyst with high activity for degradation of organic contaminants”：この文献は、熱水プロセス及びアニール処理による亜鉛タングステン酸化物の合成方法に関する。成果は、気相におけるホルムアルデヒド分解用触媒であり、これは本発明とは処理方法が異なり、金属酸化物組成が異なる。加えて、この文献は金属酸化物ナノ繊維膜の安定性開発について記載がない。 Non-patent document 2: “ZnWO 4 photocatalyst with high activity for degradation of organic contaminants”: This document relates to a method for synthesizing zinc tungsten oxide by a hydrothermal process and an annealing treatment. The result is a catalyst for formaldehyde decomposition in the gas phase, which differs from the present invention in the treatment method and in the metal oxide composition. In addition, this document does not describe the stability development of metal oxide nanofiber membranes.
非特許文献３:”ZnWO4-TiO2 composite nanofilms: Preparation, morphology, structure and photoluminescent enhancement”:この文献は、ガラス基材への浸漬堆積法による二酸化チタン及び亜鉛タングステン酸化物の合成に関する。加えて、この文献は、オートクレーブ法でナノスフェア形状のナノ繊維表面に金属をドーピングすることにも関し、これは本発明とは異なる合成方法である。加えて、この文献は金属酸化物ナノ繊維膜の安定性の開発について記載がない。 Non-Patent Document 3: “ZnWO 4 —TiO 2 composite nanofilms: Preparation, morphology, structure and photoluminescent enhancement”: This document relates to the synthesis of titanium dioxide and zinc tungsten oxide by immersion deposition on glass substrates. In addition, this document also relates to doping metal on the surface of nanospheres in the shape of nanospheres by an autoclave method, which is a synthesis method different from the present invention. In addition, this document does not describe the development of the stability of metal oxide nanofiber membranes.
特許文献１：”Nanoparticles containing titanium oxide”:この特許文献は、直径２００ｎｍ未満のアナターゼ結晶構造の二酸化チタンナノ粒子に合成に関する。加えて、この文献はオートクレーブ法でナノ繊維表面へナノスフェアの形で金属ドーピングすることにも関するが、本発明とは合成方法及び組成が異なる。加えて、この文献は金属酸化物ナノ繊維膜の安定性の開発について記載がない。 Patent Document 1: “Nanoparticles containing titanium oxide”: This patent document relates to synthesis of anatase crystal structure titanium dioxide nanoparticles with a diameter of less than 200 nm. In addition, this document also relates to metal doping in the form of nanospheres on the nanofiber surface by the autoclave method, but the synthesis method and composition differ from the present invention. In addition, this document does not describe the development of the stability of metal oxide nanofiber membranes.
特許文献２：”Metal or metal oxide deposited fibrous materials”: この特許文献は、静電噴射法による多孔質基材上への金属酸化物及び金属ナノ粒子の埋め込みに関し、本発明とは合成方法及び組成が異なる。加えて、この文献は金属酸化物ナノ繊維膜の安定性の開発について記載がない。
特許文献３：”Nanofiber and preparation method thereof”:この特許文献はエレクトロスピニングによるナノ繊維の製造方法に関する。エレクトロスピニング溶液は、ポリマーと金属複酸化物の混合物である。成果は、耐熱性で安定なナノ繊維であり、これは本発明とは安定な金属酸化物ナノ繊維膜の製造及び化学組成に関して異なる。
Patent Document 2: “Metal or metal oxide deposited fibrous materials”: This patent document relates to embedding metal oxides and metal nanoparticles on a porous substrate by electrostatic spraying. Is different. In addition, this document does not describe the development of the stability of metal oxide nanofiber membranes.
Patent Document 3: “Nanofiber and preparation method thereof”: This patent document relates to a method for producing nanofibers by electrospinning. The electrospinning solution is a mixture of polymer and metal double oxide. The result is a heat-resistant and stable nanofiber, which differs from the present invention with respect to the production and chemical composition of a stable metal oxide nanofiber film.
上記の結論として、本発明と同じ材料プロセス又は化学組成を示す非特許文献又は特許文献はない。本発明は、貴金属で修飾された二酸化チタン及び亜鉛タングステン酸化物ナノ繊維及びナノ繊維膜の製造に関する。開示されるナノ繊維及びナノ繊維膜は、可撓性で、安定で、容易に製造でき、可視光、ＵＶ及び太陽光で作用する。本発明は、化学組成及び金属酸化物ナノ繊維膜の安定性において他の製造方法と異なる特定の組成物から製造される。 In conclusion, there is no non-patent or patent document showing the same material process or chemical composition as the present invention. The present invention relates to the production of titanium dioxide and zinc tungsten oxide nanofibers and nanofiber membranes modified with noble metals. The disclosed nanofibers and nanofiber membranes are flexible, stable, easily manufacturable and operate in visible light, UV and sunlight. The present invention is manufactured from a specific composition that differs from other manufacturing methods in chemical composition and stability of the metal oxide nanofiber membrane.
本発明は、可撓性で、安定で、容易に製造でき、かつ可視光、ＵＶ及び太陽光で活性である、貴金属で修飾された二酸化チタン及び亜鉛タングステン酸化物ナノ繊維（nanofibers）及びナノ繊維膜（nanofibrous membranes）の開発にある。開示されるナノ繊維及びナノ繊維膜は他のナノ繊維及びナノ繊維膜とは光触媒組成、多機能性、高強度及び可撓性において異なる。開示される高い比表面積及び多孔性のナノ繊維は、ニードル式エレクトロスピニング、ナノスパイダーエレクトロスピニング及び強制／遠心スピニングのそれぞれからの溶液式方法によって製造することができる。 The present invention relates to noble metal modified titanium dioxide and zinc tungsten oxide nanofibers and nanofibers that are flexible, stable, easily manufactured and active in visible light, UV and sunlight. In development of nanofibrous membranes. The disclosed nanofibers and nanofiber membranes differ from other nanofibers and nanofiber membranes in photocatalytic composition, multifunctionality, high strength and flexibility. The disclosed high specific surface area and porous nanofibers can be produced by solution methods from needle electrospinning, nanospider electrospinning and forced / centrifugal spinning, respectively.
本発明は、二酸化チタン及び亜鉛タングステン酸化物をナノ繊維の主成分とし、ナノ繊維表面に亜鉛タングステン酸化物ナノロッドを有する、安定で設計どおりの金属酸化物光触媒ナノ繊維の開発に関する。加えて、ナノ繊維及び亜鉛タングステン酸化物ナノロッドの表面は単層堆積物の形の貴金属ナノ粒子で修飾されている。 The present invention relates to the development of stable and designed metal oxide photocatalyst nanofibers having titanium dioxide and zinc tungsten oxide as the main components of nanofibers and having zinc tungsten oxide nanorods on the nanofiber surface. In addition, the surfaces of the nanofibers and zinc tungsten oxide nanorods are modified with noble metal nanoparticles in the form of monolayer deposits.
光触媒ナノ繊維は、２種の主金属酸化物成分（二酸化チタン及び亜鉛タングステン酸化物）からなり、平均直径１００〜２００ナノメートルである。二酸化チタンの結晶性はアナターゼ形とルチル形の２種混合相からなる。仮焼プロセス中に、アナターゼ形の比がルチル形に関して好ましく創出された。文献によれば、アナターゼ結晶はルチル結晶と比べてＵＶ光下でより良好な光触媒活性を示すと報告されている。他方、亜鉛タングステン酸化物はサンマルチナイト（sanmatinite）であった。主金属酸化物成分とは別に、亜鉛タングステン酸化物ナノロッド（３０〜５０ナノメートル）がナノ繊維の表面に見出された。 The photocatalytic nanofiber consists of two main metal oxide components (titanium dioxide and zinc tungsten oxide) and has an average diameter of 100 to 200 nanometers. The crystallinity of titanium dioxide consists of two mixed phases, anatase and rutile. During the calcining process, a ratio of the anatase form was preferably created for the rutile form. According to the literature, anatase crystals are reported to show better photocatalytic activity under UV light than rutile crystals. On the other hand, the zinc tungsten oxide was sanmatinite. Apart from the main metal oxide component, zinc tungsten oxide nanorods (30-50 nanometers) were found on the surface of the nanofibers.
本発明のナノ繊維は、ＵＶ，可視光又は自然太陽光活性化下での光堆積法により貴金属ナノ粒子で修飾されており、この方法は容易であり、コスト効果性、高効率である。光堆積プロセス後、ナノ繊維表面上の貴金属ナノ粒子は１〜１５ナノメートルの直径を有した。本発明の貴金属ナノ粒子はパラジウム、白金、銀、金、ロジウム、エルビウム（eridium）、ルテニウム、オスミウム、タンタル、チタン又はこれらの金属の混合物から選択できる。 The nanofibers of the present invention are modified with noble metal nanoparticles by a photodeposition method under UV, visible light or natural sunlight activation, which is easy, cost effective and highly efficient. After the photodeposition process, the noble metal nanoparticles on the nanofiber surface had a diameter of 1-15 nanometers. The noble metal nanoparticles of the present invention can be selected from palladium, platinum, silver, gold, rhodium, eridium, ruthenium, osmium, tantalum, titanium or mixtures of these metals.
本発明のナノ繊維は、高い耐熱性を有するナノ繊維を容易に可撓性で安定なナノ繊維膜に製造できたので、広範囲の用途に適用できる。この膜の可撓性に関する特性は折られまたは曲げられた形状（bending shape）に従う能力であった。その可撓性とは別に、この膜は５００〜９００℃の範囲の高温に耐えることができた。金属酸化物ナノ繊維及びナノ繊維膜のこれらの特性から、この膜の用途としてベンゼン、トルエン又は亜酸化窒素などの燃焼副生ガスを浄化する乗物の触媒コンバータが期待される。空気清浄化用途のほかに、ナノ繊維及びナノ繊維膜は廃水浄化にも応用できるであろう。 The nanofibers of the present invention can be applied to a wide range of applications because nanofibers having high heat resistance can be easily produced into a flexible and stable nanofiber membrane. The flexibility property of this membrane was its ability to follow a bent or bent shape. Apart from its flexibility, the membrane was able to withstand high temperatures in the range of 500-900 ° C. From these properties of metal oxide nanofibers and nanofiber membranes, vehicle catalytic converters that purify combustion by-product gases such as benzene, toluene or nitrous oxide are expected as applications for this membrane. Besides air purification applications, nanofibers and nanofiber membranes could also be applied to wastewater purification.
本発明の金属酸化物ナノ繊維を慣用の金属酸化物ナノ繊維と比べたとき、ＷＯ３ナノ繊維はナノ繊維に高い多孔性を有し、それが高い脆性の主な原因となることが不可避である。しかしながら、本発明のＴｉＯ２−ＺｎＷＯ４ナノ繊維は他の金属酸化物と比べて高い可撓性と安定な物理的特性を有する。その結果、ＴｉＯ２−ＺｎＷＯ４ナノ繊維は金属酸化物ナノ繊維の固有の欠点を克服でき、安定な金属酸化物膜を製造できた。 When the metal oxide nanofibers of the present invention are compared with conventional metal oxide nanofibers, the WO 3 nanofibers have high porosity in the nanofibers, which is inevitably the main cause of high brittleness. is there. However, the TiO 2 —ZnWO 4 nanofibers of the present invention have high flexibility and stable physical properties compared to other metal oxides. As a result, TiO 2 —ZnWO 4 nanofibers were able to overcome the inherent disadvantages of metal oxide nanofibers and to produce stable metal oxide films.
本発明による、二酸化チタン、亜鉛タングステン酸化物、及び亜鉛タングステン酸化物ナノロッドを含み、貴金属で修飾されたナノ繊維及びナノ繊維膜の製造方法は、下記を含む。
ａ）最初に官能性ポリマーをエタノールに０．１〜４０：０．１〜４０の比で、室温３０分間で溶解して、官能性ポリマー溶液を配合した。官能性ポリマーは、炭化水素骨格に沿って水酸基、アミン基又はカルボン酸基などの官能基を有し、代表的にはポリアクリロニトリル、ポリビニルピロリドン、ポリビニルアルコール、ポリヒドロキシプロピルメタクリレート、ポリヒドロキシエチルメタクリレート、ポリグリセロールメタクリレート、又はこれらの官能性ポリマーの混合物であるポリマーから選択できた。次いで、官能性ポリマー溶液を、チタン、タングステン及び亜鉛の錯体など、少なくとも３種の金属錯体（metal complexes）の有機溶剤溶液と混合した。この金属錯体溶液は、各金属錯体を溶剤に０．１〜４０：０．１〜４０の比で室温１０分間溶解して調製できた。混合プロセスは、最初にタングステン錯体溶液を官能性ポリマー溶液に添加してから、その混合物に亜鉛及びチタン錯体溶液のそれぞれを磁気攪拌しながら３０分間添加した。金属錯体溶液の金属成分は、チタン、パラジウム、白金、銀、金、亜鉛、銅、鉄、タングステン、又はこれらの元素の混合物から選択できた。
A method for producing nanofibers and nanofiber membranes comprising titanium dioxide, zinc tungsten oxide, and zinc tungsten oxide nanorods and modified with a noble metal according to the present invention includes the following.
a) First, the functional polymer was dissolved in ethanol at a ratio of 0.1-40: 0.1-40 at room temperature for 30 minutes to formulate a functional polymer solution. The functional polymer has a functional group such as a hydroxyl group, an amine group, or a carboxylic acid group along the hydrocarbon skeleton, and is typically polyacrylonitrile, polyvinyl pyrrolidone, polyvinyl alcohol, polyhydroxypropyl methacrylate, polyhydroxyethyl methacrylate, The polymer could be selected from polyglycerol methacrylate, or a polymer that is a mixture of these functional polymers. The functional polymer solution was then mixed with an organic solvent solution of at least three metal complexes such as titanium, tungsten and zinc complexes. This metal complex solution was prepared by dissolving each metal complex in a solvent at a ratio of 0.1-40: 0.1-40 for 10 minutes at room temperature. In the mixing process, the tungsten complex solution was first added to the functional polymer solution, and then each of the zinc and titanium complex solutions was added to the mixture for 30 minutes with magnetic stirring. The metal component of the metal complex solution could be selected from titanium, palladium, platinum, silver, gold, zinc, copper, iron, tungsten, or a mixture of these elements.
ｂ）ａ）の溶液を、酢酸、硫酸、塩酸又はこれらの酸の混合物から選ばれた濃酸と０．１〜３０：０．１〜３０の重量比で混合した。
ｃ）ｂ）の溶液から、ニードル式エレクトロスピニング、ナノスパイダーエレクトロスピニング又は強制／遠心スピニングにより、ナノ繊維を製造した。
ｄ）ｃ）のナノ繊維膜を、非拘束、繊維ガラス拘束又はガラススライド拘束して、アニール及び仮焼プロセス(ＡＣプロセス)で、金属酸化物ナノ繊維膜に処理した。仮焼温度は１〜２４時間１００〜９００℃から選択できた。
ｅ）ｃ）のナノ繊維又はｄ）の金属酸化物ナノ繊維を、可視光、ＵＶ又は太陽光の下１〜２４時間の光堆積法で、貴金属ナノ粒子で修飾した。
ｆ）ｅ）のナノ繊維又はナノ繊維膜を洗浄及び乾燥した。
b) The solution of a) was mixed with a concentrated acid selected from acetic acid, sulfuric acid, hydrochloric acid or a mixture of these acids in a weight ratio of 0.1-30: 0.1-30.
c) Nanofibers were produced from the solution of b) by needle electrospinning, nanospider electrospinning or forced / centrifugal spinning.
d) The nanofiber membrane of c) was processed into a metal oxide nanofiber membrane by an annealing and calcining process (AC process) with unconstrained, fiberglass restraint or glass slide restraint. The calcining temperature could be selected from 100 to 900 ° C. for 1 to 24 hours.
e) Nanofibers from c) or metal oxide nanofibers from d) were modified with noble metal nanoparticles by photodeposition for 1-24 hours under visible light, UV or sunlight.
f) The nanofiber or nanofiber membrane of e) was washed and dried.
ａ）の有機溶剤はメチルアルコール、エチルアルコール、ジクロロメタン、ジメチルホルムアミド、ジメチルスルホキシド、クロロホルム又はトルエンから選ばれることができた。しかしながら、最も適当な溶剤はジメチルホルムアミドであった。 The organic solvent of a) could be selected from methyl alcohol, ethyl alcohol, dichloromethane, dimethylformamide, dimethyl sulfoxide, chloroform or toluene. However, the most suitable solvent was dimethylformamide.
次のセクションで本発明を説明するが、その実施例には限定されない。 The following section describes the invention, but is not limited to the examples.
ナノ繊維製造のためのエレクトロスピニング溶液の適当な組成物の開発
このセクションにおいては、所望の金属錯体溶液を混合して溶液の適当な組成物の開発を検討してから、混合後の安定性を検討した（例１〜４）。
Development of a suitable composition of electrospinning solution for nanofiber production In this section, the development of a suitable composition of solution by mixing the desired metal complex solution is considered, and then the stability after mixing is examined. It examined (Examples 1-4).
例１：
タングステン及び亜鉛錯体の水及びエタノール混合溶液からのナノ繊維の製造
二酸化チタンナノ粒子（Ｐ−２５）は水又はエタノールに可溶であるから、最初にメタタングステン酸アンモニウム水和物と酢酸亜鉛水和物を含むナノ繊維製造の検討を行ってから、Ｐ−２５を溶液混合物に添加した。
Example 1:
Preparation of nanofibers from a mixed solution of tungsten and zinc complexes in water and ethanol Since titanium dioxide nanoparticles (P-25) are soluble in water or ethanol, first ammonium metatungstate hydrate and zinc acetate hydrate After studying the production of nanofibers containing P-25, P-25 was added to the solution mixture.
前駆体溶液調整及びナノ繊維製造：
ａ）ポリビニルピロリドン（ＰＶＰ）溶液（ＰＶＰ：エタノールの重量比１：１０）にメタタングステン酸アンモニウム水和物（ＡＭＴ）錯体溶液（ＡＭＴ：水の重量比１：１０）及び酢酸亜鉛水和物（ＺＡＨ）錯体溶液（ＺＡＨ：水の重量比１：１０）を混合した。
ｂ）ａ）の溶液から、ナノスパイダー機を用い、電極グラウンド間距離１８ｃｍ、電圧４０ｋＶ，電極回転速度８ｒｐｍで、ナノ繊維膜を製造した。
ｃ）ｂ）のナノ繊維膜を特性評価した。
Preparation of precursor solution and nanofiber production:
a) Polyvinylpyrrolidone (PVP) solution (PVP: ethanol weight ratio 1:10) to ammonium metatungstate hydrate (AMT) complex solution (AMT: water weight ratio 1:10) and zinc acetate hydrate ( ZAH) complex solution (ZAH: water weight ratio 1:10) was mixed.
b) A nanofiber membrane was produced from the solution a) using a nanospider machine at an electrode ground distance of 18 cm, a voltage of 40 kV, and an electrode rotation speed of 8 rpm.
c) The nanofiber membrane of b) was characterized.
結果：ＡＭＴ及びＺＡＨ錯体溶液を含む溶液混合物は安定であり、均一なナノ繊維を製造できた（図１ａ）。 Results: The solution mixture containing the AMT and ZAH complex solutions was stable and could produce uniform nanofibers (FIG. 1a).
例２：
タングステン錯体、亜鉛錯体及び二酸化チタンナノ粒子の水及びエタノール混合物溶液からのナノ繊維の製造
この例は、ＡＭＴ及びＺＡＨ錯体溶液に二酸化チタンナノ粒子を混合後のナノ繊維の安定性及び物理的特性を調べるための実験であった。
Example 2:
Preparation of Nanofibers from Tungsten Complex, Zinc Complex and Titanium Dioxide Nanoparticles in Water and Ethanol Mixture Solution This example is to investigate the stability and physical properties of nanofibers after mixing titanium dioxide nanoparticles in AMT and ZAH complex solutions It was an experiment.
前駆体溶液調整及びナノ繊維製造：
ａ）ポリビニルピロリドン（ＰＶＰ）溶液（ＰＶＰ：エタノールの重量比１：１０）に、磁気攪拌しながら３０〜６０分間でメタタングステン酸アンモニウム水和物（ＡＭＴ）錯体溶液（ＡＭＴ：水の重量比１：１０）、酢酸亜鉛水和物（ＺＡＨ）錯体溶液（ＺＡＨ：水の重量比１：１０）及び二酸化チタンナノ粒子（Ｐ−２５：ＰＶＰ溶液の重量比１：１０）を混合した。
ｂ）ａ）の溶液から、ナノスパイダー機を用い、電極グラウンド間距離１８ｃｍ、電圧４０ｋＶ，電極回転速度８ｒｐｍで、ナノ繊維膜を製造した。
ｃ）ｂ）のナノ繊維膜を、ナノ繊維内の炭素含分を分解するために大気圧、５００℃で、４時間仮焼した後、得られた金属酸化物ナノ繊維の安定性及び物理的特性を評価した。
Preparation of precursor solution and nanofiber production:
a) A solution of ammonium metatungstate hydrate (AMT) in a polyvinyl pyrrolidone (PVP) solution (PVP: ethanol weight ratio 1:10) with magnetic stirring for 30 to 60 minutes (AMT: water weight ratio 1) : 10), zinc acetate hydrate (ZAH) complex solution (ZAH: water weight ratio 1:10) and titanium dioxide nanoparticles (P-25: PVP solution weight ratio 1:10) were mixed.
b) A nanofiber membrane was produced from the solution a) using a nanospider machine at an electrode ground distance of 18 cm, a voltage of 40 kV, and an electrode rotation speed of 8 rpm.
c) Stability and physical properties of the metal oxide nanofibers obtained after calcining the nanofiber membrane of b) for 4 hours at 500 ° C. under atmospheric pressure to decompose the carbon content in the nanofibers. Characteristics were evaluated.
結果：ナノ繊維の表面は粗に見えたが（図１ｂ）、多分、Ｐ−２５の溶解性が低いので、ＡＭＴ及びＺＡＨナノ繊維に沿って粒子凝集したためである。 Result: The surface of the nanofibers appeared rough (FIG. 1b), but probably because of the low solubility of P-25, the particles aggregated along the AMT and ZAH nanofibers.
仮焼後、ナノ繊維は、高い脆性を示し（図１ｃ）、その一部はＰ−２５の凝集物を含むので不均一な繊維構造を有する。 After calcination, the nanofibers are highly brittle (FIG. 1c) and have a non-uniform fiber structure because some of them contain P-25 aggregates.
この例から、Ｐ−２５を溶液混合物に添加すると、溶液安定性を阻害し、仮焼中のナノ繊維の形成に悪影響があり、得られる材料はさらに使用するには不適当になると結論され得た。 From this example, it can be concluded that the addition of P-25 to the solution mixture inhibits solution stability, adversely affects the formation of nanofibers during calcination, and the resulting material is unsuitable for further use. It was.
例３：
タングステン錯体、亜鉛錯体及びチタンイソプロポキシド溶液の水及びエタノール混合溶液からのナノ繊維の製造
この例は、Ｐ−２５の代わりにチタンイソプロポキシドを用いた後のナノ繊維の安定性及び物理的特性を調べるための実験であった。
Example 3:
Preparation of nanofibers from a mixed solution of tungsten and zinc complexes and titanium isopropoxide in water and ethanol This example illustrates the stability and physical properties of nanofibers after using titanium isopropoxide instead of P-25 It was an experiment to investigate the characteristics.
ナノ繊維の製造プロセスは下記を含んだ。
ａ）ポリビニルピロリドン（ＰＶＰ）溶液（ＰＶＰ：エタノールの重量比１：１０）に、メタタングステン酸アンモニウム水和物（ＡＭＴ）錯体溶液（ＡＭＴ：水の重量比１：１０）、酢酸亜鉛水和物（ＺＡＨ）錯体溶液（ＺＡＨ：水の重量比１：１０）及びチタンイソプロポキシド（ＴＩＰ）溶液（ＴＩＰ：ＰＶＰ溶液の比１：５）をそれぞれ混合した。
ｂ）ａ）の溶液から、ナノスパイダー機を用い、電極グラウンド間距離１８ｃｍ、電圧４０ｋＶ，電極回転速度８ｒｐｍで、ナノ繊維膜を製造した。
ｃ）ｂ）のナノ繊維を、ナノ繊維内の炭素含分を分解するために大気圧、５００℃で、４時間仮焼した後、得られた金属酸化物ナノ繊維の安定性及び物理的特性を評価した。
The nanofiber manufacturing process included:
a) Polyvinylpyrrolidone (PVP) solution (PVP: ethanol weight ratio 1:10), ammonium metatungstate hydrate (AMT) complex solution (AMT: water weight ratio 1:10), zinc acetate hydrate (ZAH) complex solution (ZAH: water weight ratio 1:10) and titanium isopropoxide (TIP) solution (TIP: PVP solution ratio 1: 5) were mixed respectively.
b) A nanofiber membrane was produced from the solution a) using a nanospider machine at an electrode ground distance of 18 cm, a voltage of 40 kV, and an electrode rotation speed of 8 rpm.
c) Stability and physical properties of the resulting metal oxide nanofibers after calcining the nanofibers of b) for 4 hours at 500 ° C. at atmospheric pressure to decompose the carbon content in the nanofibers Evaluated.
結果：ＴＩＰ溶液をＡＭＴ及びＺＡＨ錯体溶液に添加後、ＴＩＰが白色固体粒子に凝集して、溶液を不均一にした。 Results: After adding the TIP solution to the AMT and ZAH complex solutions, the TIP aggregated into white solid particles, making the solution non-uniform.
製造後、ナノ繊維は、使用に適さず、溶液中の固体部分がエレクトロスピニングプロセスを阻害するので、膜に製造できなかった（図１e）。その後、仮焼プロセス後に粗な凝集粒子が見られ、ナノ繊維は見られなかった（図１ｆ）。 After manufacture, nanofibers were not suitable for use and could not be made into membranes because the solid portion in solution hindered the electrospinning process (Figure 1e). Thereafter, coarse aggregated particles were seen after the calcination process, and no nanofibers were seen (FIG. 1f).
例４：
タングステン錯体、亜鉛錯体及びチタンイソプロポキシドのジメチルホルムアミド溶液からのナノ繊維の製造
この例は、ＡＭＴ，ＺＡＨ及びＴＩＰ溶液を溶解可能であるジメチルホルムアミド（ＤＭＦ）を溶液として用いた後のナノ繊維の安定性及び物理的特性を調べるための実験であった。最初に、ＴＩＰ凝集を誘導する可能性があるので、系から水を除去した。しかしながら、エタノール溶剤だけでは酢酸亜鉛を溶解するには不十分であった。追加の溶剤が必要であったので、ＤＭＦを選択した。
Example 4:
Preparation of nanofibers from a dimethylformamide solution of tungsten complex, zinc complex and titanium isopropoxide This example shows the nanofibers after using dimethylformamide (DMF) as a solution, which can dissolve AMT, ZAH and TIP solutions. It was an experiment to investigate the stability and physical properties. Initially, water was removed from the system as it may induce TIP aggregation. However, ethanol solvent alone is insufficient to dissolve zinc acetate. Since additional solvent was required, DMF was selected.
ナノ繊維製造は下記を含んだ。
ａ）ポリビニルピロリドン（ＰＶＰ）溶液（ＰＶＰ：エタノールの重量比１：１０）に、メタタングステン酸アンモニウム水和物（ＡＭＴ）錯体溶液（ＡＭＴ：ＤＭＦの重量比１：１０）、酢酸亜鉛水和物（ＺＡＨ）錯体溶液（ＺＡＨ：ＤＭＦの重量比１：１０）及びチタンイソプロポキシド（ＴＩＰ）溶液（ＴＩＰ：ＤＭＦ溶液の比１：５）をそれぞれ混合した。
ｂ）ａ）の溶液に濃酢酸を１：５の比で添加した。
ｃ）ｂ）の溶液から、ナノスパイダー機を用い、電極グラウンド間距離１８ｃｍ、電圧４０ｋＶ，電極回転速度８ｒｐｍで、ナノ繊維膜を製造した。
ｄ）ｃ）のナノ繊維を、大気圧、指定の温度で、４時間仮焼した。
５００℃（例４ａ）
６００℃（例４ｂ）
７００℃（例４ｃ）
ｅ）例４ａ、４ｂ及び４ｃで指定される金属酸化物ナノ繊維膜を評価した。
Nanofiber manufacturing included:
a) Polyvinylpyrrolidone (PVP) solution (PVP: ethanol weight ratio 1:10), ammonium metatungstate hydrate (AMT) complex solution (AMT: DMF weight ratio 1:10), zinc acetate hydrate (ZAH) complex solution (ZAH: DMF weight ratio 1:10) and titanium isopropoxide (TIP) solution (TIP: DMF solution ratio 1: 5) were mixed, respectively.
b) Concentrated acetic acid was added to the solution of a) in a ratio of 1: 5.
c) A nanofiber membrane was produced from the solution of b) using a nanospider machine at an electrode ground distance of 18 cm, a voltage of 40 kV, and an electrode rotation speed of 8 rpm.
d) The nanofibers of c) were calcined at atmospheric pressure and a specified temperature for 4 hours.
500 ° C (Example 4a)
600 ° C. (Example 4b)
700 ° C (Example 4c)
e) The metal oxide nanofiber membranes specified in Examples 4a, 4b and 4c were evaluated.
結果：３つの化学組成物ＡＭＴ，ＺＡＨ及びＴＩＰのすべてが、エタノール及びＤＭＦ混合物に、一緒に溶解可能であった。製造後にナノ繊維の特性は均一であることが示された（図２ａ）。 Results: All three chemical compositions AMT, ZAH and TIP were soluble together in the ethanol and DMF mixture. The properties of the nanofibers were shown to be uniform after production (FIG. 2a).
例４ａ：
５００℃仮焼後に、ナノ繊維の特性は仮焼前のそれと類似することが示された（図２ｂ）。ＥＤＸ分析により、ナノ繊維内にタングステン、亜鉛及びチタンが存在することが証明された（図２ｃ）。Ｘ線回析メータ（ＸＲＤ）分析によれば、チタン結晶構造の大部分はアナターゼ形であり、小部分がルチル形であった。加えて、タングステン及び亜鉛の元素を表す信号は有意ではなかった（図２ｄ）。
Example 4a:
After calcination at 500 ° C., the nanofiber properties were shown to be similar to that before calcination (FIG. 2b). EDX analysis demonstrated the presence of tungsten, zinc and titanium in the nanofiber (FIG. 2c). According to X-ray diffraction meter (XRD) analysis, the majority of the titanium crystal structure was anatase and the minor was rutile. In addition, the signals representing the elements of tungsten and zinc were not significant (FIG. 2d).
例４ｂ：
仮焼温度を６００℃に上げ、例４ａと同じ溶液を使用すると、ナノ繊維表面からロッド様構造物が突出した（図３ａ）。透過型電子顕微鏡（ＴＥＭ）で粒子観察すると（図３ｃ）、ｄ間隔値はロッド様構造物が亜鉛タングステン酸化物であろうことを示唆した（図３ｄ）。加えて、ＥＤＸ分析により、５００℃仮焼の試料から予想されるものと同様のすべての元素の存在が確認された（図３ｅ）。
Example 4b:
When the calcining temperature was raised to 600 ° C. and the same solution as in Example 4a was used, a rod-like structure protruded from the nanofiber surface (FIG. 3a). When particles were observed with a transmission electron microscope (TEM) (FIG. 3c), the d-spacing value suggested that the rod-like structure would be zinc tungsten oxide (FIG. 3d). In addition, EDX analysis confirmed the presence of all elements similar to those expected from a 500 ° C. calcined sample (FIG. 3e).
ＸＲＤから、チタン結晶の大部分はアナターゼ形であり、小部分がルチル形であった。加えて、タングステン及び亜鉛成分の証左は例４ａのそれらと比べて高い強度を示した。信号をデータベースの情報と比較して、ＺｎＷＯ４の存在が確認された（図３ｆ）。 From XRD, the majority of the titanium crystals were anatase and the minor was rutile. In addition, the evidence of tungsten and zinc components showed higher strength than those of Example 4a. The presence of ZnWO 4 was confirmed by comparing the signal with the information in the database (FIG. 3f).
例４ｃ：
７００℃仮焼後に、ナノ繊維の物理的及び化学的特性は例４ｂのそれと同様であることが示された（図３ｂ）。しかしながら、試料ではアナターゼ結晶の量がルチル形の量より少なかった。
Example 4c:
After calcination at 700 ° C., the physical and chemical properties of the nanofibers were shown to be similar to that of Example 4b (FIG. 3b). However, in the sample, the amount of anatase crystals was less than the amount of rutile form.
例２〜４のうち、例４（４ａ〜４ｃ）が最も均一で物理的に安定なナノ繊維であった。さらに、３つの例のうち、例４ｂを、優れた光触媒活性を有するアナターゼ結晶構造の量が大きいので、後の貴金属堆積プロセスのために選択した。 Of Examples 2-4, Example 4 (4a-4c) was the most uniform and physically stable nanofiber. Furthermore, of the three examples, Example 4b was chosen for a subsequent noble metal deposition process because of the large amount of anatase crystal structure with excellent photocatalytic activity.
結論として、例４ｂを次の例の貴金属堆積プロセス及びナノ繊維安定性増加のために選択した。 In conclusion, Example 4b was chosen for the following example noble metal deposition process and increased nanofiber stability.
産業的規模の適用のためのナノ繊維膜の安定性向上法
このセクションは、金属酸化物ナノ繊維の脆性が産業的製造及び更なる開発の妨げになっている事実に鑑みて、ナノ繊維膜の安定性及び可撓性の開発を検討した。なお、例４ｂの６００℃仮焼後に、得られた金属酸化物ナノ繊維膜（ＭＯＮＭ）は、仮焼前のナノ繊維膜（図４ａ）とは大きく異なり、激しく変形し、破砕されていた（図４ｂ）。この観察から、仮焼プロセスにおけるポリマーの急激な分解が不安定な金属酸化物膜の主な原因であると仮定できた。
Methods for improving the stability of nanofibrous membranes for industrial scale applications This section is based on the fact that the brittleness of metal oxide nanofibres has hindered industrial manufacturing and further development. The development of stability and flexibility was studied. In addition, after the 600 degreeC calcining of Example 4b, the obtained metal oxide nanofiber film (MONM) was greatly different from the nanofiber film before calcining (FIG. 4a), and was deformed severely and was crushed ( FIG. 4b). From this observation, it can be assumed that the rapid decomposition of the polymer in the calcination process is the main cause of the unstable metal oxide film.
以下の検討の焦点は、例４ｂが最も安定な金属酸化物ナノ繊維を製造する最も適当な試料であるので、仮焼における例４ｂの構造的安定性の開発にある。この開発の焦点は、ナノ繊維を完全な金属酸化物に完全に変換する仮焼プロセスにある。 The focus of the following discussion is on developing the structural stability of Example 4b in calcining because Example 4b is the most suitable sample for producing the most stable metal oxide nanofibers. The focus of this development is on the calcining process that completely converts the nanofibers into complete metal oxides.
例５：
タングステン錯体、亜鉛錯体及びチタンイソプロポキシドのジメチルホルムアミド溶液の仮焼前の多段アニール工程によるナノ繊維膜の製造
この製造方法は、例４ｂのそれと同様であるが、６００℃４時間の仮焼前に、含まれるポリマーのＴｇより低い温度（１００℃）、又はポリマーのＴｇより高い温度で（２００℃）で、１時間アニール工程を有した。ここで、
Example 5:
Production of nanofibrous film by multi-stage annealing step before calcination of dimethylformamide solution of tungsten complex, zinc complex and titanium isopropoxide This production method is similar to that of Example 4b, but before calcination at 600 ° C. for 4 hours And an annealing step for 1 hour at a temperature lower than the Tg of the included polymer (100 ° C.) or higher than the Tg of the polymer (200 ° C.). here,
例５ａ：
１００℃及び６００℃でのアニール及び仮焼プロセス（ＡＣプロセス）の間、非拘束のナノ繊維膜。
例５ｂ：
２００℃及び６００℃でのアニール及び仮焼プロセス（ＡＣプロセス）の間、非拘束のナノ繊維膜。
例５ｃ：
１００℃及び６００℃でのアニール及び仮焼プロセス（ＡＣプロセス）の間、繊維ガラスで平坦にサンドイッチ拘束したナノ繊維膜。
例５ｄ：
２００℃及び６００℃でのアニール及び仮焼プロセス（ＡＣプロセス）の間、繊維ガラスで平坦にサンドイッチ拘束したナノ繊維膜。
例５ｅ：
２００℃及び６００℃でのアニール及び仮焼プロセス（ＡＣプロセス）の間、ガラススライドで平坦にサンドイッチ拘束したナノ繊維膜。
例５ｆ：
折った又は曲げた形状（bending shape）に繊維ガラスで拘束したナノ繊維膜。
例５ｇ：
湾曲形状（curvy shape）に繊維ガラスで拘束したナノ繊維膜。
Example 5a:
Nanofiber membranes unconstrained during 100 ° C. and 600 ° C. annealing and calcining processes (AC process).
Example 5b:
Nanofiber membranes unconstrained during annealing and calcining processes (AC process) at 200 ° C. and 600 ° C.
Example 5c:
Nanofiber membrane flat sandwich sandwiched with fiberglass during 100 ° C and 600 ° C annealing and calcining processes (AC process).
Example 5d:
Nanofiber membrane flat sandwich sandwiched with fiberglass during 200 ° C and 600 ° C annealing and calcining processes (AC process).
Example 5e:
Nanofiber membrane flat sandwich sandwiched with glass slide during annealing and calcining process (AC process) at 200 ° C and 600 ° C.
Example 5f:
A nanofiber membrane constrained with fiberglass in a bent or bent shape.
Example 5g:
A nanofiber membrane constrained by fiberglass in a curvy shape.
結果：
例５ａ：
仮焼後のＭＯＮＭは膜の端部に少しそり（deflection）があり（図４ｄ）、仮焼前のナノ繊維膜と比較できた（図４ｃ）。
例５ｂ：
仮焼後のＭＯＮＭ表面は膜の端部のそり観察に関して例５ａ（１００℃アニール）と同様であり（図４ｆ）、仮焼前のナノ繊維膜と比較できた（図４e）。
例５ａ及び５ｂでは、追加のアニールプロセスでＭＯＮＭのそりの程度は減少できるが、膜の物理的不安定性を完全には克服できなかった。
result:
Example 5a:
The MONM after calcination had a slight deflection at the end of the film (FIG. 4d), which was comparable to the nanofiber film before calcination (FIG. 4c).
Example 5b:
The MONM surface after calcination was similar to Example 5a (100 ° C. anneal) with respect to warping of the edge of the film (FIG. 4f) and could be compared with the nanofiber film before calcination (FIG. 4e).
In Examples 5a and 5b, the additional annealing process could reduce the degree of MONM warpage, but could not completely overcome the physical instability of the film.
例５ｃ：
仮焼後のＭＯＮＭ表面では、破片は観察されず平坦に見えた（図４ｈ）。加えて、膜の寸法は仮焼前に対して７１．４３％減少した（図４ｇ）。
例５ｄ：
仮焼後のＭＯＮＭは例５ｃと同様であるが、膜の表面は平坦（図４ｊ）から粗な構造（図４ｉ）に変化した。膜の寸法は６８．８３％減少し、例５ｄより物理的に安定であることを示唆した。
例５ｃ及び５ｄでは、ＡＣプロセスと繊維ガラスによる構造拘束の組み合わせにより安定性が増加したＭＯＮＭが得られた（図５ａ及び５ｃ）。
Example 5c:
On the surface of the MONM after calcination, no debris was observed and it appeared flat (FIG. 4h). In addition, the dimensions of the film decreased by 71.43% compared to that before calcination (FIG. 4g).
Example 5d:
The MONM after calcination was the same as in Example 5c, but the film surface changed from flat (FIG. 4j) to a rough structure (FIG. 4i). The membrane size was reduced by 68.83%, suggesting that it was physically more stable than Example 5d.
Examples 5c and 5d resulted in MONMs with increased stability due to the combination of the AC process and fiberglass structural constraints (FIGS. 5a and 5c).
例５ｅ：
ナノ繊維膜は仮焼前（図４ｋ）及び仮焼後（図４ｌ）の両方で平滑な表面を有した。しかしながら、仮焼後の膜は脆くて、破断されて全ピース（a whole piece）として拾えた。
例５ｅから、繊維ガラスを拘束に用いるとガラススライドより良好であると結論された（図５ｂ及び５ｄ）。
例５ｆ：
一対の繊維ガラスで膜をビーカの内部に沿って湾曲して拘束して、仮焼後のナノ繊維膜の可撓性を調べた（図４ｍ）。このプロセスではＭＯＮＭの形状を望むように維持できることが見出された（図４ｎ）。
例５ｇ：
例５ｆと同じ条件で仮焼前にナノ繊維膜を繊維ガラスの積層中にラップして、仮焼後のナノ繊維膜の可撓性を調べた（図４о）。仮焼後に膜は非常に安定であり、低角度で折りまたは曲げても（bending）亀裂は観察されなかった（図４ｐ）。
Example 5e:
The nanofiber membrane had a smooth surface both before calcination (FIG. 4k) and after calcination (FIG. 4l). However, the calcined film was brittle and was broken and picked up as a whole piece.
From Example 5e it was concluded that fiberglass was better than a glass slide when used for restraint (FIGS. 5b and 5d).
Example 5f:
The membrane was bent and restrained along the inside of the beaker with a pair of fiber glasses, and the flexibility of the nanofiber membrane after calcination was examined (FIG. 4m). It has been found that this process can maintain the MONM shape as desired (FIG. 4n).
Example 5g:
Under the same conditions as in Example 5f, the nanofiber membrane was wrapped in a fiberglass laminate before calcination, and the flexibility of the nanofiber membrane after calcination was examined (FIG. 4о). After calcination, the film was very stable and no cracks were observed when bent or bent at low angles (FIG. 4p).
金属酸化物ナノ繊維膜への貴金属の光堆積
この検討の目的は、可視光及び太陽光による活性化に関して、金属酸化物ナノ繊維の光触媒の活性を改良することであった。貴金属で修飾された金属酸化物ナノ繊維の開発は、表面にパラジウム及び白金などの貴金属をドープして行うことができた。
ＵＶ，可視光及び自然太陽光での光堆積法によるこの貴金属ドープのために、例４ｂを選択した。
Photodeposition of noble metals on metal oxide nanofiber films The purpose of this study was to improve the photocatalytic activity of metal oxide nanofibers with respect to activation by visible light and sunlight. Development of metal oxide nanofibers modified with noble metals could be achieved by doping the surface with noble metals such as palladium and platinum.
Example 4b was chosen for this noble metal doping by photodeposition with UV, visible light and natural sunlight.
例６：
ＵＶ，可視光及び自然太陽光でのナノ繊維への貴金属修飾
ナノ繊維への貴金属修飾は下記のように処理した。
ａ）硝酸パラジウム（ＩＩ）水和物及び水素ヘキサクロロ白金酸（ＩＶ）金属錯体溶液の調製方法：
第１のビーカで、水に硝酸パラジウム（ＩＩ）水和物を磁気攪拌しながら１０分間０．００１６７：１０の比（重量％）で添加した。
第２のビーカで、水に水素ヘキサクロロ白金酸（ＩＶ）を磁気攪拌しながら１０分間０．００５：１０の比（重量％）で添加した。
ｂ）ａ）の２つの混合物を混合してから、例５ｄのナノ繊維を添加して１時間各種の光源で照射した。ここで、
ＵＶ光（例６ａ）
可視光（例６ｂ）
太陽光（例６ｃ）
ｃ）例６ａ〜６ｃのナノ繊維を洗浄及び乾燥した。
ｄ）ｃ）のナノ繊維及び堆積した貴金属ナノ粒子を評価した。
Example 6:
Modification of noble metal to nanofibers with UV, visible light and natural sunlight was performed as follows.
a) Preparation method of palladium (II) nitrate hydrate and hydrogen hexachloroplatinic acid (IV) metal complex solution:
In a first beaker, palladium (II) nitrate hydrate was added to water at a ratio (wt%) of 0.00167: 10 for 10 minutes with magnetic stirring.
In a second beaker, hydrogen hexachloroplatinic acid (IV) was added to water at a ratio (wt%) of 0.005: 10 for 10 minutes with magnetic stirring.
b) After mixing the two mixtures of a), the nanofibers of Example 5d were added and irradiated with various light sources for 1 hour. here,
UV light (Example 6a)
Visible light (Example 6b)
Sunlight (Example 6c)
c) The nanofibers of Examples 6a-6c were washed and dried.
d) The nanofibers and deposited noble metal nanoparticles of c) were evaluated.
結果：
例６ａ：
ＵＶ光によるパラジウム及び白金イオンの還元及び金属酸化物ナノ繊維へのそれぞれの貴金属の核形成は、光源と溶液との距離で制御した。反応後、得られたナノ繊維の特性は反応前のナノ繊維のそれと同様であった。しかしながら、ナノ繊維の平均直径は増加した（図６ａ）。ＥＤＸから、ナノ繊維の表面にパラジウムと白金の両方の元素が確認された（図６ｄ）。
result:
Example 6a:
The reduction of palladium and platinum ions by UV light and the nucleation of each noble metal on the metal oxide nanofibers were controlled by the distance between the light source and the solution. After the reaction, the properties of the obtained nanofibers were similar to those of the nanofibers before the reaction. However, the average diameter of the nanofibers increased (Figure 6a). EDX confirmed both palladium and platinum elements on the surface of the nanofiber (FIG. 6d).
例６ｂ：
可視光で同様の光還元反応を実施した。反応後に、ナノ繊維の特性は例６ａのそれと同様であった（図６ｂ）。加えて、ＥＤＸ分析からナノ繊維の表面にパラジウムと白金の両方の元素が同様に確認された。
Example 6b:
A similar photoreduction reaction was carried out with visible light. After the reaction, the nanofiber properties were similar to those of Example 6a (FIG. 6b). In addition, EDX analysis confirmed both palladium and platinum elements on the nanofiber surface as well.
例６ｃ：
実験中光強度を記録しながら自然太陽光で光還元反応を実施した。反応後にナノ繊維の平均直径は増大し、ＥＤＸ分析により表面に例６ａ及び６ｂの場合より多くの金属元素が観察された（図６ｃ）。
Example 6c:
The photoreduction reaction was carried out with natural sunlight while recording the light intensity during the experiment. The average diameter of the nanofibers increased after the reaction, and more metal elements were observed on the surface than in Examples 6a and 6b by EDX analysis (FIG. 6c).
次に金属酸化物ナノ繊維上に堆積した金属ナノ粒子をＴＥＭで評価できた。二酸化チタン及び亜鉛タングステン酸化物上に金属ナノ粒子が均一に分散していた（図６ｅ）。粒子のｄ間隔の分析によりパラジウムナノ粒子の寸法は１〜１５ナノメートルの間であると報告された（図６ｆ）。亜鉛タングステン酸化物上の白金ナノ粒子（図６ｇ）はＴＥＭにより３ナノメートル未満であると観察された（図６ｈ）。 Next, the metal nanoparticles deposited on the metal oxide nanofibers could be evaluated by TEM. Metal nanoparticles were uniformly dispersed on titanium dioxide and zinc tungsten oxide (FIG. 6e). Analysis of the d spacing of the particles reported that the size of the palladium nanoparticles was between 1 and 15 nanometers (FIG. 6f). Platinum nanoparticles on zinc tungsten oxide (FIG. 6g) were observed by TEM to be less than 3 nanometers (FIG. 6h).
例６の結果から、可視光、ＵＶ及び太陽光で有効な光還元反応が行われたことが分かる。結論として、最適な例及び将来の規模拡大のために最も適当なプロセスは、それぞれの光還元が太陽光で成功裏に実施されたこと（自由エネルギー）、例６ａ及び６ｂより容易に実施できることから、例６ｃであった。 From the results of Example 6, it can be seen that an effective photoreduction reaction was performed with visible light, UV, and sunlight. In conclusion, the best example and the most appropriate process for future scale-up is that each photoreduction was successfully carried out with sunlight (free energy), which is easier to implement than Examples 6a and 6b. Example 6c.
ナノ繊維膜によるモデル汚染物の光触媒分解
汚染物分解効率を、モデル汚染物としてのメチレンブルー（ＭＢ）の光触媒分解により測定した。最初に、１０ｍｇのナノ繊維を自然太陽光下で５００ｐｐｍＭＢ溶液に懸濁した（図７）。
Photocatalytic degradation of model contaminants by nanofiber membranes The degradation efficiency of contaminants was measured by photocatalytic degradation of methylene blue (MB) as a model contaminant. First, 10 mg of nanofibers were suspended in a 500 ppm MB solution under natural sunlight (FIG. 7).
実験では、２種のナノ繊維：ＴｉＯ２−ＺｎＷＯ４及びＰｄ／Ｐｔ−ＴｉＯ２−ＺｎＷＯ４を、それぞれ別に、光触媒効率の比較のために用いた。また、触媒なしのＭＢ溶液を対照として用いた。 In the experiment, two types of nanofibers: TiO 2 —ZnWO 4 and Pd / Pt—TiO 2 —ZnWO 4 were used separately for comparison of photocatalytic efficiency. An MB solution without catalyst was used as a control.
結果：
両方のナノ繊維が高いＭＢ分解効率を示した。Ｐｄ／Ｐｔ−ＴｉＯ２―ＺｎＷＯ４及びＴｉＯ２−ＺｎＷＯ４のナノ繊維では、最も高いＭＢ分解効率は最初の２時間においてみられた（図７）。
result:
Both nanofibers showed high MB degradation efficiency. For Pd / Pt—TiO 2 —ZnWO 4 and TiO 2 —ZnWO 4 nanofibers, the highest MB degradation efficiency was seen in the first 2 hours (FIG. 7).
ナノ繊維膜の触媒活性を、気相５００ｐｐｍベンゼン（揮発性有機化合物、ＶＯＣ）に関して評価した。実験は、０．１ｇのナノ繊維を用いて、４時間、可視光下で、５００ｐｐｍのベンゼンを処理して実施した（懸濁液と電球の距離を１０ｃｍに固定）（図８ａ）。反応後、分解したベンゼンの濃度をガスクロマトグラフィ（ＧＣ）で評価した。 The catalytic activity of the nanofiber membrane was evaluated with respect to gas phase 500 ppm benzene (volatile organic compound, VOC). The experiment was carried out using 0.1 g of nanofibers and treating 500 ppm of benzene under visible light for 4 hours (distance between suspension and bulb fixed at 10 cm) (FIG. 8a). After the reaction, the concentration of decomposed benzene was evaluated by gas chromatography (GC).
結果：
ベンゼン濃度分析は、対照ガスと比較して分解したベンゼンのピーク領域を計算することで行った。分析により、対照触媒として用いたＷＯ３ナノ繊維はベンゼン分解効率を全く示さなかったが、ＴｉＯ２−ＺｎＷＯ４ナノ繊維は３７％のベンゼン分解効率であった（表１）。
result:
The benzene concentration analysis was performed by calculating the peak area of decomposed benzene compared to the control gas. Analysis showed that the WO 3 nanofibers used as the control catalyst did not show any benzene decomposition efficiency, whereas the TiO 2 —ZnWO 4 nanofibers had a benzene decomposition efficiency of 37% (Table 1).
ベンゼン分解反応とは別に、Ｐｄ／Ｐｔ−ＴｉＯ２―ＺｎＷＯ４ナノ繊維をさらにメタノールのギ酸メチルへの酸化転移のために用いた。反応後、６．４４２にＧＣピークが見られ、ＧＣデータベースで参照するとギ酸メチルのものであることが確認された（図８ｂ及び８ｃ）。 Apart from the benzene decomposition reaction, Pd / Pt—TiO 2 —ZnWO 4 nanofibers were further used for the oxidative transfer of methanol to methyl formate. After the reaction, a GC peak was observed at 6.442, which was confirmed to be that of methyl formate when referenced in the GC database (FIGS. 8b and 8c).
Claims (17)
ａ）官能性ポリマー溶液を、チタン、タングステン及び亜鉛錯体を含む少なくとも３種の金属前駆体の有機溶剤溶液と混合する。その混合プロセスは、初めにタングステン錯体溶液を官能性ポリマー溶液に加えてから、亜鉛及びチタン錯体溶液を磁気攪拌しながら３０分間加える。
ｂ）ａ）で得られる溶液を、濃酸に０．１〜３０：０．１〜３０の重量比で混合する。
ｃ）ｂ）で得られる溶液から、ニードル式エレクトロスピニング、ナノスパイダーエレクトロスピニング又は強制／遠心スピニングによって、ナノ繊維を製造する。
ｄ）ｃ）で得られるナノ繊維膜を、非拘束、繊維ガラス拘束又はガラススライド拘束で、アニール及び仮焼（ＡＣ法）する処理をして、金属酸化物ナノ繊維膜にする。仮焼温度は１〜２４時間で１００〜９００℃から選択できる。
ｅ）ｃ）で得られるナノ繊維、又はｄ）で得られる金属酸化物ナノ繊維を、可視光、ＵＶ又は太陽光の下１〜２４時間の光堆積法により、貴金属ナノ粒子で修飾する。
ｆ）ｅ）で得られるナノ繊維又はナノ繊維膜を洗浄及び乾燥する。 A method for producing a stable and designed metal oxide nanofiber and a flexible and stable nanofiber membrane according to any one of claims 1 to 10,
a) The functional polymer solution is mixed with an organic solvent solution of at least three metal precursors including titanium, tungsten and zinc complexes. The mixing process first adds the tungsten complex solution to the functional polymer solution, and then adds the zinc and titanium complex solution for 30 minutes with magnetic stirring.
b) The solution obtained in a) is mixed with concentrated acid in a weight ratio of 0.1-30: 0.1-30.
c) Nanofibers are produced from the solution obtained in b) by needle electrospinning, nanospider electrospinning or forced / centrifugal spinning.
d) The nanofiber film obtained in c) is subjected to a treatment of annealing and calcination (AC method) in a non-constraint, fiberglass restraint or glass slide restraint to form a metal oxide nanofiber film. The calcination temperature can be selected from 100 to 900 ° C. in 1 to 24 hours.
e) The nanofibers obtained in c) or the metal oxide nanofibers obtained in d) are modified with noble metal nanoparticles by a photodeposition method under visible light, UV or sunlight for 1-24 hours.
f) The nanofiber or nanofiber membrane obtained in e) is washed and dried.
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| TH1501007936 | 2015-12-29 | ||
| PCT/TH2016/000106 WO2017116316A1 (en) | 2015-12-29 | 2016-12-28 | Flexible metal oxide nanofibers prepared by electrospinning and stable nanofibrous fabric made thereof and preparation process |
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| CN113426492A (en) * | 2021-06-29 | 2021-09-24 | 东华大学 | Amorphous porous ceramic nanofiber membrane and preparation method and application thereof |
| CN113926455B (en) * | 2021-09-14 | 2024-01-23 | 河南科技大学 | Preparation method of bimetallic nanoparticle fiber catalyst |
| WO2023154872A2 (en) * | 2022-02-11 | 2023-08-17 | Drexel University | Nanomaterial-based processing of dyes and organic compounds |
| CN115449957A (en) * | 2022-10-01 | 2022-12-09 | 刘玉文 | Household textile fabric and preparation method thereof |
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| WO2006041092A1 (en) * | 2004-10-15 | 2006-04-20 | Bridgestone Corporation | Dye sensitized metal oxide semiconductor electrode and method for manufacturing the same, and dye sensitized solar cell |
| KR100921476B1 (en) * | 2007-08-29 | 2009-10-13 | 한국과학기술연구원 | Dye-sensitized solar cell with metal oxide layer composed of metal oxide nanoparticles by electrospinning and the fabrication method thereof |
| KR100945035B1 (en) * | 2008-01-29 | 2010-03-05 | 재단법인서울대학교산학협력재단 | Tungstates based visible-light induced oxides photocatalysts and synthesis methods thereof |
| US8535632B2 (en) * | 2008-03-20 | 2013-09-17 | The University Of Akron | Ceramic nanofibers containing nanosize metal catalyst particles and medium thereof |
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| KR20110034146A (en) * | 2009-09-28 | 2011-04-05 | 재단법인대구경북과학기술원 | Polycrystalline titanium dioxide nanorod and method of manufacturing the same |
| EP2614177A4 (en) * | 2010-09-10 | 2014-09-10 | Ozin Geoffrey A | Photoactive material comprising nanoparticles of at least two photoactive constiuents |
| CN103623803A (en) * | 2012-08-30 | 2014-03-12 | 上海纳晶科技有限公司 | Visible light photocatalyst and preparation method therefor |
| CN103806127A (en) * | 2012-11-15 | 2014-05-21 | 大连捌伍捌创新工场科技服务有限公司 | Photocatalysis fiber |
| JP6342225B2 (en) * | 2014-06-09 | 2018-06-13 | 国立研究開発法人物質・材料研究機構 | Photocatalyst composite material and method for producing the same |
| CN105107519A (en) * | 2015-09-11 | 2015-12-02 | 辽宁石油化工大学 | Method for synthetizing tungstate/tungsten oxide heterojunction photocatalyst in situ |
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| WO2021261531A1 (en) * | 2020-06-23 | 2021-12-30 | 国立大学法人弘前大学 | Catalyst for fuel cells, electrode catalyst layer, membrane electrode joined body, solid polymer type fuel cell, method for producing titanium oxide for catalyst carriers, and method for producing catalyst for fuel cells |
| JP2022003634A (en) * | 2020-06-23 | 2022-01-11 | 国立大学法人弘前大学 | Fuel cell catalyst, electrode catalyst layer, membrane electrode assembly, polymer electrolyte fuel cell, and manufacturing method of fuel cell catalyst |
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| CN108778499B (en) | 2022-08-12 |
| CN108778499A (en) | 2018-11-09 |
| WO2017116316A1 (en) | 2017-07-06 |
| JP6669875B2 (en) | 2020-03-18 |
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