WO2017116316A1 - Flexible metal oxide nanofibers prepared by electrospinning and stable nanofibrous fabric made thereof and preparation process - Google Patents

Flexible metal oxide nanofibers prepared by electrospinning and stable nanofibrous fabric made thereof and preparation process Download PDF

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Publication number
WO2017116316A1
WO2017116316A1 PCT/TH2016/000106 TH2016000106W WO2017116316A1 WO 2017116316 A1 WO2017116316 A1 WO 2017116316A1 TH 2016000106 W TH2016000106 W TH 2016000106W WO 2017116316 A1 WO2017116316 A1 WO 2017116316A1
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Prior art keywords
nanofibers
stable
metal oxide
flexible
nanofibrous membrane
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PCT/TH2016/000106
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English (en)
French (fr)
Inventor
Varol INTASANTA
Nakarin SUBJALEARNDEE
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National Science and Technology Development Agency
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National Science and Technology Development Agency
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Priority claimed from TH1501007936A external-priority patent/TH176227A/th
Application filed by National Science and Technology Development Agency filed Critical National Science and Technology Development Agency
Priority to JP2018534601A priority Critical patent/JP6669875B2/ja
Priority to CN201680077366.6A priority patent/CN108778499B/zh
Publication of WO2017116316A1 publication Critical patent/WO2017116316A1/en
Anticipated expiration legal-status Critical
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    • 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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Definitions

  • This invention is the development of rioble-metals decorated titanium dioxide and zinc tungstein oxide nanofibers and nanofibrous membranes which are flexible, stable and could be easily fabricated and active under visible, UV and sunlight.
  • the described nanofibers and nanofibrous membrane are different from the others nanofibers and nanofibrous membrane in terms of photocatalyst composition, multifunction properties, high strength and flexibility.
  • the described high surface area and porosity nanofibers can be fabricated by solution-based processing from both of needle-based electrospinning, nanospider electrospinning and forced/centrifuge spinning.
  • VOCs volatile organic compounds
  • photocatalysis which utilizes light as an activating energy source.
  • the photocatalysis reaction requires light for redox reaction of organic molecules suitable for unspecified organic decomposition.
  • the photocatalytic reaction can occur in both of liquid and gas phases, so the technology is very versatile and has wide range of applications.
  • many advantages of the technology support the high potential of industrial scale production such as self-cleaning property, cheap material arid low maintainance cost.
  • most of photocatalytic meterials required high activation energy which can be found mainly in UV light because the catalyst has large band gap that cannot be governed by visible light. So, this drawback may limit the industrial scale application of this technology.
  • shape and size of catalysts play an important role in the organic decomposition efficiency due to the photocatalysis reaction occurs mainly at the surface of catalysts. From this reason, nanophotocatalysts may be the most suitable materials due to their high surface area.
  • Nanofibers can overcome both of disadvantages inherent to nanoparticles and film materials with their high surface area, recyclability and non-agglomoration materials.
  • the photocatalysts must inherit antibacterial property in order to widen the range of application.
  • one of the crucial drawbacks of using photocatalyst in liquid phase is the recovery process.
  • One of the recovery processes is centrifugation method. The method is very effective in lab scale application but the industrial production and application are costly.
  • application of nanomaterials suffers from filtration process while film metrials have a drawback in low surface area.
  • photocatalyst materials from nanofibers can overcome both of problems in terms of recyclability and high surface area.
  • nanoparticle synthetic method requires high cost and non- environmentally friendly processing such as high temperature or vacuum system. This may result in increase in the production cost and time consumption.
  • Wastewater treatment requires an appropriate method by employing catalyst as main composition.
  • the photocatalysis is one of the most promising processes due to its catalyts chemical composition are low cost and able to use the natural sunlight to catalyze the reaction.
  • the photocatalysts have two main drawbacks which are limited region of catalyze light and high fragility.
  • This invention relates to the fabrication of noble metals decorated titanium dioxide and zinc tungstein oxide nanofibers and nanofibrous membrane.
  • the described nanofibers and nanofibrous membranes are stable, flexible, easily fabricated and able to work under visible, UV and natural sunlight.
  • This invention is fabricated from specific combinations that are difference from the others fabrication methods in terms of chemical composition and stability of the metal oxide nanofibers membrane.
  • nanofilms Preparation, morphology, structure and photoluminescent enhancement.
  • the literature concerned the synthesis of titanuium dioxide and zinc tungstein oxide by dip- coating method on the glass substrate that had different synthesis process from this patent.
  • the literature did not mention the metal oxide nanofibrous membrane stability development.
  • This patent concerned the synthesis of titanium dioxide nanoparticles in anatase crystal structure at diameter less than 200 nm.
  • this patent also concerned the metal doping on the nanofibers surface in form of nanosphere by autoclave technique which had different synthesis method and composition from this patent.
  • the literature did not mention the metal oxide nanofibrous membrane stability development.
  • EDX spectrum showed tungstein, zinc and titanium composition in nanofibers.
  • XRD spretrum showed crystallinity of tungstein, zinc and titanium in nanofibers.
  • EDX spectrum showed tungsten, zinc and titanium composition in nanofibers.
  • XRD spretrum showed crystallinity of tungsten, zinc and titanium in nanofibers while zinc and tungsten complexes were in form of zinc tungstein oxide (ZnW0 4 ).
  • Nanofibers after fabrication by solution in example 4b (After annealing at 100 °C and calcination at 600 °C).
  • Nanofibers after fabrication by solution in example 4b (After annealing at 100 °C and calcination at 600 °C with fiber glass sandwich).
  • Nanofibers after fabrication by solution in example 4b (Before calcination).
  • Nanofibers after fabrication by solution in example 4b (After annealing at 200 °C and calcination at 600 °C with fiber glass confinement within a beaker), m) Nanofibers after fabrication by solution in example 4b (Before calcination with fiber glass confinement in a pleating shape).
  • Nanofibers after fabrication by solution in example 4b (After annealing at 200 °C and calcination at 600 °C with fiber glass confinement in a pleating shape).
  • Figure 5 Pictures of nanofibrous membrane after calcination via SEM and TEM whereas: a) Nanofibrous membrane after calcination by fiberglass confinement process which showed freely weaving nanofibers.
  • First bottle is 500 ppm benzene (control).
  • Second bottle is 500 ppm benzene with W0 3 nanofibers.
  • Third bottle is 500 ppm benzene with Ti0 2 -ZnW0 4 nanofibers.
  • Fourth bottle is 500 ppm benzene with Pd/Pt-Ti0 2 -ZnW0 4 .
  • This invention relates to the development of stable and as-designed metal oxides photocatalytic nanofibers that composed of titanium dioxide and zinc tungsten oxide as a main composition of the nanofibers with zinc tungsten oxide nanorods on the nanofibers' surface.
  • the surface of nanofibers and zinc tungsten oxide nanorods were decorated by noble metal nanoparticles in a form of single layer deposition.
  • the photocatalytic nanofibers consisted of two main metal oxide compositions, titanium dioxide and zinc tungstein oxide, with an average diameter of 100-200 nanometers.
  • the titanium dioxide crystallinity composed of two mixed phases of anatase and rutile forms. During the calcination process, the ratio of anatase form was favorably created with respect to rutile form. It reported in literature that anatase crystal performed better photocatalytic activity under UV light than rutile crystal.
  • the zinc tungstein oxide was sanmatinite. Apart from the main metal oxide components, zinc tungstein oxide nanorods (30-50 nanometers) were found on the surface of nanofibers.
  • the nanofibers according to this invention were decorated with noble metal nanoparticles via photodeposition process under UV, visible or natural sunlight activationhat was facile, cost effective and highly efficienct. After photodeposition process, noble metal nanoparticles on the nanofibers' surface were observed with diameter of 1-15 nanometers.
  • the noble metal nanoparticles for this invention could be selected from palladium, platinum, silver, gold, rhodium, eridium, ruthenium, osmium, tantalum, titanium or mixture of these metals.
  • the nanofibers according to this invention can be applied in variety of applications because the nanofibers inherited high thermal resistance could be easily fabricated into a flexible and stable nanofibrous membrane.
  • the characteristics of the membrane related to its flexibility was the ability to be conformed into a bending shape. Apart from its flexibility, the membrane was able to tolerate high temperature in a rage of 500-900 °C. From the described properties of metal oxide nanofibers and nanofibrous membrane, promising applications of this membrane could be a catalytic converter within vehicles for purifying the combustion by-product gases such as benzene, toluene or nitrous oxide. Aprat from air purication application, the nanofibers and nanofibrous membrane could be applied for waste water purification as well.
  • WO 3 nanofibers inherited high porosity within the nanofibers which unaviodibly constituted as the main reason for high fragility.
  • Ti0 2 - ZnW0 4 nanofibers from this invention inherited high flexibility and stable physical character in comparison with others metal oxides. Consequently, the Ti0 2 -ZnW0 4 nanofibers can overcome the inherent drawback of metal oxide nanfibers and could be fabricated into stable metal oxide membranes.
  • a funtional polymer solution was first formulated by dissolving a functional polymer in ethanol in a ratio of 0.1-40: 0.1-40 at room temperature for 30 minutes.
  • the functional polymers could be selected from the polymers with functional groups along their hydrocarbon backbone such as hydroxy group, amine group or carboxylic acide group, represnting polyacrylonitrile, polyvinylpyrrolidone, polyvinylalcohol, polyhydroxypropyl methacrylate, polyhydroxyethyl methacrylate, polyglycerol methacrylate or mixture of these functional polymers.
  • the functionl polymer solution was mixed with at least 3 metal complexes such as titanium, tungsten and zinc complexes in organic solvents.
  • the metal complex solution could be prepared by dissolving the respective metal complex in a solvent in a ratio of 0.1-40: 0.1-40 under room temperature for 10 minutes.
  • the mixing process started from adding tungsten complex solution into the functional polymer solution before adding the zinc and titanium complex solution in to the mixture respectively under magnetic stirring for 30 minutes.
  • the metal components in the metal complex solution could be selected from titanium, palladium, platinum, silver, gold, zinc, copper, iron, tungsten or mixture of these elements.
  • the nanofibrous membrane from c) was processed into a metal oxide nanofibrous membrane by annealing and calcination process (AC process) under non-confinement, fiberglass or glass slide confinement.
  • the calcination temperature could be selected from 100-900 °C for 1-24 hours.
  • nanofibers from c) or metal oxide nanofibers from d) were decorated by noble metal nanoparticles via photodeposition process under visible, UV or sunlight for 1-24 hours.
  • the organic solvent in a) could be selected from methyl alcohol, ethyl alcohol, dichloromethane, dimethylformamide, dimethylsulfoxide, chloroform or toluene. However, the most suitable solvent was dimethylformamide.
  • Example 1 Fabrication of nanofibers from tungsten and zinc complex in water and ethanol mixture
  • titanium dioxide nanoparticles (P-25) was soluble in water or ethanol, the primary study of nanofiber fabrication containing ammonium metatungstate hydrate and zinc acetate hydrate was performed prior to addition of P-25 into the solution mixture.
  • PVP Polyvinylpyrroridone
  • AMT ammonium metatungstate hydrate
  • ZAH zinc acetate hydrate
  • Example 2 Fabrication of nanofibers from tungsten complex, zinc complex and titanium dioxide nanoparticles in water and ethanol mixture
  • This example was experimented in order to study the stability and physical characteristics of nanofibers after mixing the titanium dioxide nanoparticles into the AMT and ZAH complex solution.
  • PVP Polyvinylpyrroridone
  • AMT ammonium metatungstate hydrate
  • ZAH zinc acetate hydrate
  • Ti dioxide nanoparticles P-25: PVP solution in a ratio of 1:10) under magnetic stirring for 30-60 minutes.
  • nanofibers from b) was calcined under atmospheric pressure at 500 °C for 4 hours in order to decompose the carbon content within the nanofibers prior to further characterization for stability and physical characteristics of the resulting metal oxide nanofibers.
  • the nanofibers After calcination, the nanofibers showed high degree of fragility (Figure lc) with non-homcigeneous fibrous structure as some of their parts contained aggregates of P-25 ( Figure Id).
  • Example 3 Fabrication of nanofibers from tungsten complex, zinc complex and titanium isopropoxide solution in water and ethanol mixture.
  • Nanofibers fabrication process containing;
  • PVP Polyvinylpyrroridone
  • AMT ammonium metatungstate hydrate
  • ZAH zinc acetate hydrate
  • Ti titanium isopropoxide
  • TIP TIP: PVP solution in a ratio of 1:5) respectively.
  • nanofibers from b) was calcined under atmospheric pressure at 500 °C for 4 hours in order to decompose the carbon content within the nanofibers prior to further characterization for stability and physical characteristics of the resulting metal oxide nanofibers.
  • nanofibers were unusable and unable to be fabricated into membranes because the solid parts in the solution disrupted the electrospinning process (Figure le). Subsequently, rough aggregated particles were found after the calcination process and no trace of nanofibers were found (Picture If).
  • Example 4 Fabrication of nanofibers from tungsten complex, zinc complex and titanium isopropoxide in dimethylformamide.
  • Nanofibers fabrication process containing;
  • PVP Polyvinylpyrroridone
  • AMT ammonium metatungstate hydrate
  • ZH zinc acetate hydrate
  • TIP titanium isopropoxide
  • Example 4a After calcination at 500 °C, the nanofibers' characteristics was shown to be similar to their before calcination ( Figure 2b). The EDX analysis proved the existence of tungstein, zinc and titanium within the nanofibers ( Figure 2c). From
  • Example 4b After increasing the calcination temperature to 600 °C and using the same solution from example 4a, a rod-like structure stemmed out of the nanofibers surface ( Figure 3a). From particle investigation by Transmittion Electron Microscopy (TEM) ( Figure 3c), d-spacing values implied that the rod-like structure might be zinc tungstein oxide ( Figure 3d). In addition, EDX analysis confirmed the existence of all expected elements similar to those of the sample from 500 °C calcination ( Figure 3e).
  • Example 4c After calcination at 700 °C, the physical and chemical characteristics of the nanofibers was similared to that of the example 4b ( Figure 3b). However, the sample showed lower amount of anatase crystal than the amount of rutile crystal. Among the examples 2-4, example 4 (4a-4c) was the most homogeneous and physically stable nanofiber. Furthermore, example 4b was selected out of the 3 examples for subsequent noble metal deposition process because it inherited large fraction of anatase crystal structure that had excellent photocatalytic activity.
  • example 4b was selected for noble metal deposition process and increasing the nanofibers stability in the next example.
  • Nanofibrous membrane stability enhancment process for industrial scale application
  • Example 5 Fabrication of nanofibrous membrane from tungsten complex, zinc complex and titanium isopropoxide in dimethylformamide by multiple annealing steps prior to calcianation.
  • the fabrication process here was similar to that for example 4b but with an annealing step for an hour at the lower temperature than Tg of the containing polymer (100 °C) or at the temperature higher than Tg of the polymer (200 °C), before calcination at 600 °C for 4 hours whereas:
  • Example 5a Non-confinement nanofibrous membrane during annealing and calcination processes (AC processes) at 100 °C and 600 °C.
  • Example 5b Non-confinement nanofibrous membrane during annealing and calcination processes (AC processes) at 200 °C and 600 °C.
  • Example 5c Fiberglass-confinement nanofibrous membrane in a flat sandwich during annealing and calcination processes (AC processes) at 100 °C and 600 °C.
  • Example 5d Fiberglass-confinement nanofibrous membrane in a flat sandwich during annealing and calcination processes (AC processes) at 200 °C and 600 °C.
  • Example 5e Glass-slide confinement nanofibrous membrane in a flat sandwich during annealing and calcination processes (AC processes) at 200 °C and 600 °C.
  • Example Sf Fiberglass-confinement nanofibrous membrane in a bending shape.
  • Example 5g Fiberglass confinement nanofibrous membrane in a curvy shape.
  • Example 5a The MONM after calcination showed deflection in a low degree at the edge of the membrane (Figure 4d) which could be compared with the nanofibrous membrane before calcination ( Figure 4c).
  • Example 5b The MONM after calcination was similar to the example 5a
  • the additional annealing process could reduce the degree deflection in MONM but was unable to completely overcome the membrane's physical instability.
  • Example 5c The MONM's surface after calcination appeared flat with no fragments observed (Figure 4h). In addition, the membrane's size was decreased at
  • Example 5d The MONM after calcination was similar to the example 5c but the memebrane's surface changed from flat (Figure 4j) to rough stucture ( Figure 4i). The membrane's size was decreased at 68.83% rate, suggesting more physical stability than that of example 5d.
  • Example 5f The flexibility of nanofibrous membrane upon calcination was studied by using a pair of fiberglasses for membrane confinement curved along the interior of a beaker ( Figure 4m). It was found that the process could maintain the shape of MONM as desired ( Figure 4n).
  • Example 5g The flexibility of nanofibrous membrane upon calcination was also studied by wrapping the nanofibrous membrane among stacking layers of fiberglasses (Figure 4o) before calcination in the same condition as that for the example Sf . It was found that, after calcination, the membrane was very stable and no cracking was observed upon bending with such a small angle (Figure 4p).
  • the objective of this study was to improve the metal oxide nanofiber's photocatalytic activity against activation by visible light and sunlight.
  • the development of noble-metal decorated metal oxide nanofiber could be done by doping noble metals such as palladium and platinum on the surface.
  • Example 4b was selected for this noble metal doping by photodeposition process under UV, visible and natural sunlight.
  • Example 6 Noble-metal decoration on nanofibers under UV, visible and natural sunlight
  • Example 6a The reduction of palladium and platinum ions and nucleation of the respective metal on the metal oxide nanofibers under UV light were controlled by the distance between the light source and solution. After the reaction, the resulted nanofibers' characteristics was similar to that of the nanofibers before the reaction. However, the nanofibers' averaged diameter was increased ( Figure 6a). From EDX, both palladium and platinum elements were found on the nanofibers' surface ( Figure 6d).
  • Example 6b A similar photoreduction reaction was performed with visible light. After the reaction, the nanofibers' characteristics was similar to that of the example 6a ( Figure 6b). In addition, EDX analysis revealed both palladium and platinum elements on the surface as well.
  • Example 6c The photoreduction reaction was performed under natural sunlight with light intensity recorded duing the experiment. After the reaction, the nanofibers' averaged diameter was increased and more metal elements were observed on the surface than those on example 6a and 6b ( Figure 6c) as revealed by EDX analysis.
  • Metal nanoparticles deposited on the metal oxide nanofibers could then be characterized by TEM. It was found that the metal nanoparticles were dispered homogeneously on titanium dioxide and zinc tungsten oxide (Figure 6e). The sizes of palladium nanoparticles were reported to be in between 1-15 nanometers after analyzing the d-spacing of particles ( Figure 6f). Platinum nanoparticles on zinc tungsten oxide ( Figure 6g) were observed to be smaller than 3 nanometers under TEM ( Figure 6h).
  • the pollutant decomposition effieciency was measured against photocatalytic degradation of methylene blue (MB) as a model pollutant. Firstly, 10 mg of nanofibers was suspended in 500 ppm MB solution under natural sunlight (Figure 7).
  • nanofibrous membranes' catalytic activities were evaluated against gaseous
  • VOCs Volatile organic compounds

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CN110745934A (zh) * 2019-10-22 2020-02-04 庆泓技术(上海)有限公司 一种改性的高活性无机纤维复合材料和制备及再生方法
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CN114164511A (zh) * 2021-03-23 2022-03-11 耐酷时(北京)科技有限公司 一种多孔二氧化钛混合聚丙烯腈纤维的制备方法
CN114164511B (zh) * 2021-03-23 2024-02-09 耐酷时(北京)科技有限公司 一种多孔二氧化钛混合聚丙烯腈纤维的制备方法
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WO2023154872A3 (en) * 2022-02-11 2023-10-19 Drexel University Nanomaterial-based processing of dyes and organic compounds
CN116328756A (zh) * 2023-03-16 2023-06-27 东南大学 一种复合薄膜半导体光催化剂及其制备方法
CN118145600A (zh) * 2024-03-12 2024-06-07 山东大学 一种基于负载铂纳米颗粒的复合纳米纤维膜提高氢气纯度的方法
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