WO2017086722A1 - Photocatalyseur de lumière visible composite d'oxyde métallique/poly(3-hexylthiophène) cristallin ayant une activité photocatalytique de lumière visible hautement efficace, et son procédé de préparation - Google Patents

Photocatalyseur de lumière visible composite d'oxyde métallique/poly(3-hexylthiophène) cristallin ayant une activité photocatalytique de lumière visible hautement efficace, et son procédé de préparation Download PDF

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WO2017086722A1
WO2017086722A1 PCT/KR2016/013298 KR2016013298W WO2017086722A1 WO 2017086722 A1 WO2017086722 A1 WO 2017086722A1 KR 2016013298 W KR2016013298 W KR 2016013298W WO 2017086722 A1 WO2017086722 A1 WO 2017086722A1
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p3ht
metal oxide
hexylthiophene
zno
nanofiber
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Korean (ko)
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이태일
오진영
채수상
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가천대학교 산학협력단
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing

Definitions

  • the present invention relates to a composite visible photocatalyst comprising a metal oxide and a poly [3-hexyl thiophene], and more particularly to a crystalline poly [3-hexyl thiophene] adsorbed on a metal oxide and a part of the metal oxide surface. It relates to a composite visible photocatalyst comprising.
  • Zinc oxide a semiconductor oxide
  • Zinc oxide is generally used most useful for various photocatalyst applications including electrochemical catalysts, energy conversion or storage applications, and for use in various photovoltaic devices and bio / mono molecule sensors. It is a substance.
  • Zinc oxide has advantages such as biocompatibility, reproducibility of the synthesis process, long term stability, low cost and high oxidation efficiency, but its use is limited to the ultraviolet range due to the inherent wide band gap of 3.7 eV.
  • poly [3-hexylthiophene] As a material widely used among the conjugated polymers, poly [3-hexylthiophene] (P3HT) may be exemplified.
  • P3HT poly [3-hexylthiophene]
  • This material is widely used as a semiconductor polymer in the manufacture of various organic electronic products due to its easy self-organized properties and excellent electrical, optical and chemical properties.
  • P3HT exhibits a relatively high absorbance in a broad range of visible light in the wavelength range of 500 to 600 nm and can be used as a suitable detectable material in the wavelength range.
  • the electrical properties of P3HT can facilitate the transfer of charge carriers to inorganic materials, which is the most important step in the photocatalytic reaction under visible light.
  • the grafting molecular layer may be discontinuous in its inherently conjugated structure in the P3HT main chain, and thus charge transfer at the interface between the polymer and ZnO, an important factor for high efficiency of photocatalytic activity, It is excessively disturbed.
  • the present inventors studied high-efficiency P3HT / ZnO composite visible photocatalysts having high crystallinity between interfaces and which are sustainable and durable even under aqueous environmental conditions, while applying nanofiber P3HT to ZnO semiconductor nanorods at low temperature conditions. It has been found that complexing by a mixing method can produce a complex visible photocatalyst with high efficiency and durability.
  • an object of the present invention is to provide a composite visible photocatalyst comprising a metal oxide and a crystalline poly [3-hexylthiophene] adsorbed on a part of the metal oxide surface, and a method of manufacturing the same.
  • a composite visible photocatalyst comprising a metal oxide and a crystalline poly [3-hexylthiophene] adsorbed on a portion of the metal oxide surface.
  • the metal oxide may be an n-type semiconductor metal oxide series
  • the crystalline poly [3-hexylthiophene] may be a nanofiber poly [3-hexylthiophene].
  • the portion may be greater than 0 area% and less than or equal to 11.2 area%, and the crystalline poly [3-hexylthiophene] may be adsorbed in a mesh shape on the metal oxide surface.
  • step (a) mixing the organic solvent solution of the metal oxide and the organic solvent solution of crystalline poly [3-hexylthiophene] at 0 °C or less to obtain a mixture; (b) centrifuging the mixture of step (a) to remove supernatant from the condensate; (c) drying the condensate from which the supernatant obtained in step (b) has been removed; And (d) washing the dried product obtained in the step (c) with an organic solvent.
  • the metal oxide of step (a) may be an n-type semiconductor metal oxide series, wherein the crystalline poly [3-hexylthiophene] of step (a) is a nanofiber poly [3-hexylthione] Offen].
  • the organic solvent of step (a) and the organic solvent of step (d) are independently of each other xylene, toluene, benzene, dichlorobenzene, chloroform, alcohol, tetrahydrofuran, acetone, and these It may be selected from the group consisting of, wherein the below 0 °C of step (a) may be -10 °C or less.
  • the composite visible photocatalyst of the present invention showed excellent visible photocatalytic decomposition efficiency compared to the non-composite ZnO powder in the visible light decomposition efficiency measurement test; Gas decomposition activity of acetaldehyde, which is a harmful gas generated in the organic adhesive, was measured and found to decompose 90% or more of the initial acetaldehyde gas after about 20 hours, and exhibited excellent harmful component resolution; It was confirmed that even after repeated decomposition reactions with Rhodamine B (20 times), the composite visible photocatalyst maintained the resolution and was excellent in chemical durability.
  • the composite visible photocatalyst including the metal oxide / crystalline poly [3-hexylthiophene] of the present invention and a method of manufacturing the same achieve an effect of achieving excellent visible photocatalytic resolution and chemical durability, and thus in a field requiring harmful gas decomposition. It can be usefully used as the highly efficient organic-inorganic visible light composite photocatalyst system used and its easy manufacturing method.
  • FIG. 1 is a schematic diagram showing a process of preparing a nanofiber P3HT / ZnO composite visible photocatalyst.
  • FIG. 2 is a photograph showing the properties of P3HT / ZnO composite visible photocatalyst (Nanofibril P3HT / ZnO) to which nanofiber P3HT-treated zinc oxide (Bare ZnO) and nanofiber P3HT are adsorbed.
  • FIG. 3 is a scanning electron microscope (SEM) photograph of (a) and (b) before and after washing nanofiber P3HT / ZnO composite visible photocatalyst with meta-xylene. A schematic diagram showing a state in which fiber P3HT is adsorbed).
  • FIG. 4 is a scanning electron microscope (SEM) measurement photograph (10,000 ⁇ ) of a nanofiber P3HT / ZnO composite visible photocatalyst surface (transmission electron microscope) of the white dotted circle portion of (a), (a) TEM) photo (600,000 ⁇ ) (insertion shows composition distribution of white dotted circle portion in (a)) (b), and transmission electron microscope (TEM) photo of white dotted circle portion in (a) (1,200,000 x) (c).
  • SEM scanning electron microscope
  • FIG. 5 shows nanofiber P3HT / ZnO composite visible-catalyst (As-deposited), and solvent (toluene, meta-xylene, tetrahydrofuran, THF), acetone before washing process. ]) Absorption spectrum of the nanofiber P3HT / ZnO composite visible photocatalyst after washing with water.
  • P3HT / ZnO composite visible photocatalyst is a graph showing the results of photocatalytic activity against visible light.
  • FIG. 7 is a scanning electron microscope (SEM) photograph of a nanofiber P3HT / ZnO composite visible photocatalyst according to the increase in the amount of nanofiber P3HT and the surface occupancy in the preparation of the nanofiber P3HT / ZnO composite photocatalyst (left) Inset is a photograph of a ZnO solution or nanofiber P3HT / ZnO composite visible photocatalyst solution, and the right inset is a schematic diagram of the state in which nanofiber P3HT is adsorbed on the surface of zinc oxide.
  • SEM scanning electron microscope
  • FIG. 8 shows absorbance spectra (a) of ZnO, P3HT (2.09%) / ZnO, P3HT (4.79%) from nanofiber P3HT / ZnO composite visible photocatalysts with increasing ZnO surface occupancy of nanofiber P3HT. ) / ZnO, P3HT (8.0%) / ZnO, P3HT (11.2%) / ZnO] and photoluminescence (PL) (P3HT [top]: uncomplexed P3HT itself, Nanibril P3HT / ZnO [bottom]) : Measurement result of nanofiber P3HT / ZnO composite visible photocatalyst (b) having a surface occupancy of 11.2%.
  • FIG. 9 is a graph (a) and the degree of decomposition of acetaldehyde gas as a result of measuring photocatalytic activity (C / C 0 ) of visible light of nanofiber P3HT / ZnO composite visible photocatalyst with increasing ZnO surface occupancy rate of nanofiber P3HT; a [C / C 0 (CH3CHO) ] resulting graph (b) of measuring the.
  • 10 is a graph showing the results of 20 consecutive visible light (550 nm) decomposition reactions using Rhodamine B for nanofiber P3HT / ZnO composite visible photocatalyst.
  • the present invention provides a composite visible photocatalyst comprising a metal oxide and a crystalline poly [3-hexylthiophene] adsorbed on a portion of the metal oxide surface.
  • the metal oxide may be used without limitation as long as it is a conductive or semiconductor material.
  • the metal oxide is based on an n-type semiconductor metal oxide, for example, zinc oxide, titanium oxide (TiO 2 ), or the like.
  • the zinc oxide may be chemically synthesized and used, for example, by using a hydrolytic sol-gel reaction of zinc nitrate hexahydrate and hexamethylenetetraamine. ] Or commercially available zinc oxide may be used.
  • the crystalline poly [3-hexylthiophene] refers to a poly [3-hexylthiophene] that is not amorphous, and may preferably be a poly [3-hexylthiophene] on a nanofiber.
  • the nanofiber poly [3-hexylthiophene] can be prepared by crystallization in a poly [3-hexylthiophene] solution.
  • nanofiber-like P3HT can be prepared by cooling a solution of P3HT and heating it to room temperature.
  • the portion of the metal oxide surface on which the crystalline poly [3-hexylthiophene] is adsorbed in the composite visible photocatalyst may be greater than 0 area% and no more than 11.2 area%, wherein the crystalline poly [3-hexylthiophene] is It may be adsorbed in a mesh shape on the metal oxide surface.
  • the composite visible photocatalyst of the present invention exhibited about 80% of visible light decomposition efficiency after 300 minutes, compared to about 40% of visible light decomposition efficiency after 300 minutes of non-complex ZnO powder in the visible light decomposition efficiency measurement test. , Good visible light decomposition efficiency; Gas decomposition activity of acetaldehyde, which is a harmful gas generated in the organic adhesive, was measured and found to decompose 90% or more of the initial acetaldehyde gas after about 20 hours, and exhibited excellent harmful component resolution; After repeated decomposition reactions with Rhodamine B (20 times), the composite visible photocatalyst maintained the resolution and was found to be excellent in chemical durability.
  • the present invention comprises the steps of (a) mixing the organic solvent solution of the metal oxide and the organic solvent solution of the crystalline poly [3-hexylthiophene] at 0 °C or less to obtain a mixture; (b) centrifuging the mixture of step (a) to remove supernatant from the condensate; (c) drying the condensate from which the supernatant obtained in step (b) has been removed; And (d) provides a method for producing a composite visible photocatalyst comprising the step of washing the dried product obtained in step (c) with an organic solvent.
  • Step (a) is a step of mixing the organic solvent solution of each material so that the crystalline poly [3-hexylthiophene] can be adsorbed on the surface of the metal oxide.
  • the metal oxide may be used as long as it is a conductive or semiconducting material.
  • the metal oxide may be an n-type semiconductor metal oxide series, for example, zinc oxide, titanium oxide (TiO 2 ), or the like.
  • the crystalline poly [3-hexylthiophene] refers to a poly [3-hexylthiophene] that is not amorphous, and may preferably be a poly [3-hexylthiophene] on a nanofiber.
  • step (a) the metal oxide surface occupancy ratio of the finally obtained composite photocatalyst is determined according to the mixing ratio of poly [3-hexylthiophene] mixed with the metal oxide, and the total weight of the P3HT / metal oxide composite photocatalyst is determined.
  • P3HT 2.4, 7.3, 14.6, and 24.2 wt% are mixed, a composite visible photocatalyst corresponding to P3HT area occupancy of 2.09, 4.79, 8.00, and 11.2 area%, respectively can be obtained. That is, a catalyst having excellent photolysis efficiency may be prepared according to the amount of P3HT nanofibers mixed in step (a).
  • the maximum saturated surface occupancy obtained by this method was 11.2% (which can be obtained when mixed with P3HT 24.2 wt%), and it was confirmed that the photocatalytic efficiency at this time was the highest.
  • the organic solvent of step (a) is not limited as long as it is an organic solvent that dissolves without damaging the poly [3-hexylthiophene], preferably xylene, toluene, benzene, dichlorobenzene, chloro Foam, alcohol, tetrahydrofuran, acetone, and mixtures thereof.
  • Step (a) is a step of forming a crystalline nanofiber form through a self-assembly method by performing a mixing process at a low temperature state. Specifically, in the low temperature state, the solubility of the polymer in the solution is lowered, thereby increasing the interaction between the poly [3-hexylthiophene] polymer chain in the solution, poly [3- hex having molecular regularity Silthiophene] The polymer chain is self-assembled by increased interaction.
  • Step (b) removes the supernatant from the condensate by centrifuging the mixture of step (a) to remove unbound P3HT nanofibers that are not bound to the metal oxide surface and P3HT nanofibers that are weakly bound to the metal oxide surface. It is a process of removal.
  • Step (c) is a step of drying the condensate from which the supernatant liquid obtained in step (b) has been removed. It can be dried to obtain a composite visible photocatalyst powder.
  • Step (d) is a step of washing the dried product obtained in step (c) with an organic solvent, wherein the organic solvent used is not limited as long as it is an organic solvent that dissolves without damaging the poly [3-hexylthiophene], preferably Preferably xylene, toluene, benzene, dichlorobenzene, chloroform, alcohol, tetrahydrofuran, acetone, and mixtures thereof.
  • the organic solvent used is not limited as long as it is an organic solvent that dissolves without damaging the poly [3-hexylthiophene], preferably Preferably xylene, toluene, benzene, dichlorobenzene, chloroform, alcohol, tetrahydrofuran, acetone, and mixtures thereof.
  • a homogeneous pre-prepared P3HT fiber prepared in a poor solvent at low temperature was mixed with ZnO nanorods under the same conditions at low temperature.
  • the conformation maintains its own crystal structure without transitioning to the disordered domain, thereby exhibiting high visible light-catalytic activity under irradiation. do.
  • ZnO sub-microrods were prepared as described below using a hydrothermal process. Specifically, 0.42-0.21 g of zinc nitrate hexahydrate was dissolved in 100 mL of deionized water at room temperature, and 0.24-1.2 g of hexamethylenetetraamine (HMTA) was dissolved in 100 mL of deionized water to prepare two precursor solutions. . Transfer the zinc nitrate solution (zinc precursor solution) to two syringes, transfer the HMTA solution to a 250 mL round flask, and use a syringe pump to pump 100 mL of zinc precursor solution contained in the syringe with vigorous stirring at 85 ° C.
  • HMTA hexamethylenetetraamine
  • Nanofiber P3HT (0.01 to 2.0 wt% based on the total amount of meta-xylene solvent) was prepared by alternately cooling and heating the 1D crystal seed of P3HT in a meta-xylene solution of P3HT.
  • the solution was placed in a double jacketed ethanol cooler with two necks. The ethanol was circulated to the cooler and the cooling rate changed with the temperature of the cooler. The temperature of the solution was measured by a thermometer through the neck provided in the cooler. After the temperature of the solution was cooled to ⁇ 20 ° C., the solution was taken out and left in air to bring the temperature to room temperature (25 ° C.).
  • the prepared ZnO nanowire powder was dispersed in meta-xylene (m mg / mL) using a sonicator for 30 minutes (1 mg / mL), and then cooled for 10 minutes ( ⁇ 10 ° C.).
  • the meta-xylene dispersion of ZnO and the meta-xylene solution of nanofibers P3HT which were prepared while maintaining the temperature of ⁇ 10 ° C., were prepared at a predetermined concentration (to the total weight of P3HT / ZnO nanofibers).
  • P3HT 2.4, 7.3, 14.6, and 24.2 wt%) and vigorously stirred for 2 hours.
  • Non-composite ZnO nanowire powders and the nanofiber P3HT / ZnO composite visible photocatalyst obtained above were applied to a 10 cm ⁇ 10 cm glass plate and the photographed results are shown in FIG. 2.
  • ZnO is grayish white
  • the nanofiber P3HT / ZnO composite visible photocatalyst shows purple color.
  • the prepared nanofiber P3HT / ZnO composite visible photocatalyst was washed three times using meta-xylene as a solvent by centrifugation at 3,000 RPM.
  • the surface of the nanofiber P3HT / ZnO composite visible photocatalyst before and after the cleaning process was observed with a field emission scanning electron microscopy (FE-SEM, JEOL 6300). Indicated. As shown in FIG. 3, when the meta-xylene washing process is performed, the surface of the complex visible photocatalyst having undergone the washing process compared to the complex visible photocatalyst surface image (see FIG. 3 (a)) before performing the washing process [FIG.
  • the nanofiber P3HT is formed in a mesh shape on the surface of ZnO, and the area of ZnO exposed on the surface of the P3HT / ZnO composite visible photocatalyst compared to the composite visible photocatalyst before the washing process is performed. It can be seen that the ratio is significantly increased.
  • the washing process was performed on the P3HT / ZnO composite visible photocatalyst prepared by using amorphous P3HT. As a result, all of the amorphous P3HT was lost from the ZnO surface to obtain a composite visible photocatalyst in which the amorphous P3HT was adsorbed on the ZnO surface. It was not possible (data not shown).
  • a red color representing Zn and a blue color representing the S component of the P3HT molecule appear adjacent to each other, indicating that the P3HT molecule is adsorbed onto the ZnO surface.
  • Figure 4 (c) it can be seen that the P3HT on the surface of the P3HT / ZnO composite photocatalyst form a crystalline fiber having an interplanar distance of about 0.361 nm.
  • Optical analysis was performed using a UV-vis spectrophotometer (Jasco, V-670).
  • the nanofiber P3HT / ZnO composite visible photocatalyst and the nanofiber P3HT / ZnO composite visible photocatalyst prior to the washing process were treated with a solvent (toluene, meta-xylene, m-Xylene, tetrahydrofuran, THF, acetone Acetone]) and the absorption spectrum of the nanofiber P3HT / ZnO composite visible photocatalyst after washing is shown in FIG.
  • a solvent toluene, meta-xylene, m-Xylene, tetrahydrofuran, THF, acetone Acetone
  • the absorption spectrum of the nanofiber P3HT / ZnO composite visible photocatalyst before the washing process shows a maximum absorbance at about 500 nm, similar to the previous literature (Macromolecules, Vol. 45, pp. 7504-7513, 2012). It was. Also, even after washing the P3HT / ZnO composite visible catalyst with an organic solvent, the absorption spectrum was similar to that before the washing, and it was found that the complexed adsorption state was not changed even after the organic solvent washing process.
  • Photocatalytic activity against visible light of the nanofiber P3HT / ZnO composite visible photocatalyst was evaluated as follows.
  • the non-composited ZnO powder exhibited about 40% visible light decomposition efficiency after 300 minutes.
  • Nanofiber P3HT / ZnO composite visible photocatalyst (f-P3HT) without cleaning process showed lower efficiency than amorphous P3HT / ZnO composite visible photocatalyst (P3HT), but nanofiber P3HT / ZnO composite visible photocatalyst (P3HT) washing f-P3HT) showed about 80% of visible light decomposition efficiency at 300 minutes, and was confirmed to show the best visible light decomposition efficiency.
  • the absorbance spectrum and photoluminescence (PL) measurement results of the nanofiber P3HT / ZnO composite visible photocatalyst with increasing ZnO surface occupancy rate of the nanofiber P3HT are shown in FIG. 8.
  • Photoluminescence measurements were performed using a photoluminescence spectrometer (photoluminescence, Perkin Elmer, LS55).
  • the absorbance tended to increase as the ZnO surface occupancy rate of the nanofiber P3HT was increased (see FIG. 8 (a)).
  • uncomplexed P3HT exhibited relatively high PL Quenching strength
  • nanofiber P3HT / ZnO composite visible photocatalyst showed relatively low PL strength. This is presumed to be due to charge-transfer at the interface of ZnO of P3HT complexed in the case of the composite visible photocatalyst, which supports the mechanism related to the visible photocatalytic reaction of the nanofiber P3HT / ZnO composite visible photocatalyst.
  • the photocatalytic activity of the complex visible photocatalyst on the decomposition of acetaldehyde was evaluated as a change in gas concentration under the following conditions.
  • GASTEC GV-100 Gas Detectro Tube
  • the visible photocatalytic degradation activity of the nanofiber P3HT / ZnO composite visible photocatalyst through the decomposition reaction with respect to acetaldehyde gas was measured and is shown in FIG. 9 (b).
  • FIG. 9 (b) when the nanofiber P3HT / ZnO composite visible photocatalyst was reacted with the visible photocatalyst, it was measured to decompose 90% or more of the initial acetaldehyde gas after about 20 hours. It was confirmed that the resolution of harmful components of the photocatalyst was excellent.

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Abstract

La présente invention concerne : un photocatalyseur de lumière visible composite comprenant un oxyde métallique et du poly(3-hexylthiophène) cristallin, qui est adsorbé au niveau d'une partie de la surface de l'oxyde métallique ; et son procédé de préparation. Le photocatalyseur de lumière visible composite comprenant un oxyde métallique et du poly(3-hexylthiophène) cristallin et son procédé de préparation, selon la présente invention, obtiennent un effet mettant en œuvre une excellente capacité de dégradation photocatalytique de lumière visible et une excellente durabilité chimique et, de ce fait, la présente invention peut être utile comme système de photocatalyseur composite de lumière visible organique-inorganique hautement efficace à utiliser dans un domaine nécessitant une décomposition de gaz nocif, et comme procédé pour le préparer facilement.
PCT/KR2016/013298 2015-11-18 2016-11-17 Photocatalyseur de lumière visible composite d'oxyde métallique/poly(3-hexylthiophène) cristallin ayant une activité photocatalytique de lumière visible hautement efficace, et son procédé de préparation WO2017086722A1 (fr)

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