WO2024053969A1 - Procédé de fabrication de filtre de photocatalyseur composite activé par lacune d'oxygène, et filtre associé de purification d'air - Google Patents

Procédé de fabrication de filtre de photocatalyseur composite activé par lacune d'oxygène, et filtre associé de purification d'air Download PDF

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WO2024053969A1
WO2024053969A1 PCT/KR2023/013184 KR2023013184W WO2024053969A1 WO 2024053969 A1 WO2024053969 A1 WO 2024053969A1 KR 2023013184 W KR2023013184 W KR 2023013184W WO 2024053969 A1 WO2024053969 A1 WO 2024053969A1
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composite photocatalyst
filter
catalyst
activated
oxygen vacancies
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Korean (ko)
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박현웅
박지연
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경북대학교 산학협력단
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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
    • 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
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • 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
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2027—Metallic material
    • B01D39/2031—Metallic material the material being particulate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • 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
    • 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
    • B01J21/063—Titanium; 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
    • B01J23/16—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
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic 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
    • B01J37/08—Heat treatment
    • 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
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0471—Surface coating material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/10—Filtering material manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20776—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/802—Photocatalytic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide

Definitions

  • the present invention relates to a method of manufacturing a composite photocatalyst filter activated by oxygen vacancies and the resulting air purifying filter. More specifically, a method of manufacturing a composite photocatalyst filter activated by oxygen vacancies of tungsten oxide and titanium dioxide and the resulting air purification filter. It's about filters.
  • thermal oxidation using metal and metal oxide catalysts can convert environmental pollutants into carbon dioxide and water that are harmless to the human body, but since the thermal oxidation method is carried out at a high temperature of 200°C or higher, an additional device that can supply heat energy is required. . This limits the practical application of thermal oxidation methods.
  • environmental pollutants can be converted into carbon dioxide and water that are harmless to the human body using light energy, a non-polluting energy source.
  • photocatalysts the biggest advantage of photocatalysts is that the reaction can be carried out at room temperature using light energy without requiring an additional energy source.
  • Photocatalysts can sterilize, antibacterial, and decompose contaminants in the air and solutions, so they can be used in glass, tiles, exterior walls, food, factory interior walls, metal products, water tanks, marine pollution purification, construction materials, mold prevention, UV protection, water purification, and air purification. It is used for a wide range of purposes.
  • the most widely used material as a photocatalyst is titanium dioxide. Titanium dioxide is advantageous from an economic perspective because it can be used semi-permanently. Additionally, since titanium dioxide is a safe material that does not have a negative impact on the environment, there is no concern about secondary pollution when disposed of. Republic of Korea Patent No. 10-1606642 discloses a visible light-responsive photocatalyst with hydrophilic surface modification using polymer materials, but there was a problem of increasing the activity of the photocatalyst.
  • the purpose of the present invention is to provide a method for manufacturing a composite photocatalyst filter activated by oxygen vacancies.
  • the purpose is to provide an air purifying filter manufactured according to the above manufacturing method.
  • a first step of preparing a Black-WO 3 (BW) catalyst by heat treating tungsten oxide powder at a temperature range of 400 to 600 ° C. under a reducing gas atmosphere;
  • a second step of preparing a Black-TiO 2 (BT) catalyst by heat-treating the powder mixed by adding a reducing agent to titanium dioxide at a temperature range of 200 to 400 ° C. under an inert gas atmosphere;
  • a method for manufacturing a composite photocatalyst filter activated by oxygen vacancies is provided, which removes carbon monoxide from the surrounding environment during filter adsorption.
  • the present invention provides an air purifying filter manufactured according to the above manufacturing method.
  • the manufacturing method of the present invention produces a composite photocatalyst in a simple manner in a relatively short time, and can increase the photoactivity of the tungsten oxide and titanium dioxide composite photocatalyst activated by oxygen vacancies compared to a single catalyst.
  • the composite photocatalyst produced according to the production method of the present invention has the advantage of improved light absorption and charge separation, and is suitable for removing indoor air pollution due to its high optical activity.
  • Figure 1 shows catalyst changes as the firing maintenance period increases according to an embodiment of the present invention.
  • Figure 2 shows the light absorption wavelength range and catalyst color change of tungsten oxide and titanium dioxide improved with oxygen vacancies according to an embodiment of the present invention.
  • Figure 3 shows TEM images of tungsten oxide (W), titanium dioxide (T), tungsten oxide (BW) activated with oxygen vacancies, and titanium dioxide (BT) catalysts according to an embodiment of the present invention.
  • Figure 4 shows XRD of tungsten oxide (W), titanium dioxide (T), tungsten oxide (BW) activated with oxygen vacancies, and titanium dioxide (BT) catalysts according to an embodiment of the present invention.
  • FIG. 6 shows W 4f, Ti 2p It was done.
  • Figure 7 shows a comparison of the removal performance of tungsten oxide (W), titanium dioxide (T), tungsten oxide (BW) activated with oxygen vacancies, and titanium dioxide (BT) catalysts according to an embodiment of the present invention.
  • Figure 8 shows a comparison of performance by ratio of tungsten oxide (W), titanium dioxide (T), tungsten oxide (BW) activated with oxygen vacancies, and titanium dioxide (BT) catalysts according to an embodiment of the present invention.
  • Figure 9 shows a comparison of the carbon monoxide removal performance of tungsten oxide (W), titanium dioxide (T), tungsten oxide (BW) activated with oxygen vacancies, and titanium dioxide (BT) catalysts according to an embodiment of the present invention and the carbon monoxide oxidation It shows the carbon dioxide production rate.
  • Figure 10 shows a comparison of carbon monoxide removal reaction rates of tungsten oxide (W), titanium dioxide (T), tungsten oxide (BW) activated with oxygen vacancies, and titanium dioxide (BT) catalysts according to an embodiment of the present invention. .
  • Figure 11 shows the light absorption wavelength region of the composite photocatalyst according to an embodiment of the present invention.
  • Figure 12 shows the catalyst color of the composite photocatalyst according to an embodiment of the present invention.
  • Figure 13 shows the carbon monoxide removal and carbon dioxide production rates of a composite photocatalyst containing zeolite according to an embodiment of the present invention.
  • Figure 14 shows a comparison of carbon monoxide removal reaction rates of a composite photocatalyst containing zeolite according to an embodiment of the present invention.
  • Figure 15 shows the carbon monoxide removal and carbon dioxide production rates of a composite photocatalyst carbon nanotube filter according to an embodiment of the present invention.
  • Figure 16 shows a comparison of carbon monoxide removal reaction rates of composite photocatalyst carbon nanotube filters according to an embodiment of the present invention.
  • Figure 17 shows the carbon monoxide removal rate of the TAW composite photocatalytic filter according to a comparative example of the present invention.
  • a first step of preparing a Black-WO 3 (BW) catalyst by heat treating tungsten oxide powder at a temperature range of 400 to 600 ° C. under a reducing gas atmosphere;
  • a method for manufacturing a composite photocatalyst filter activated by oxygen vacancies is provided.
  • Tungsten oxide is a catalyst that can be expected to exhibit catalytic activity under visible light irradiation, but it has the disadvantage of low electron transfer and rapid recombination of electrons and holes, which reduces photoactivity.
  • TiO 2 photocatalyst is non-toxic, harmless to the human body, excellent durability, and abundant resources, so it is a photocatalyst widely applied in photocatalyst technology. However, it has the disadvantage of inducing a photocatalytic reaction only in the ultraviolet region, which is a specific light wavelength.
  • the filter manufacturing method of the present invention solves the shortcomings of each catalyst and increases the light absorption of the catalyst and improves conductivity by activating oxygen vacancies in the catalyst to increase performance compared to the existing catalyst.
  • tungsten oxide and titanium dioxide which have different photocharge movement speeds, or by manufacturing a composite photocatalyst of tungsten oxide and titanium dioxide activated by oxygen vacancies, it is possible to reduce the rapid recombination of electrons and holes and improve charge separation, thereby increasing photoactivity compared to existing ones. there is.
  • Tungsten oxide powder is heat-treated in a H 2 /Ar atmosphere, preferably 10% H 2 (in Ar balance), at a temperature range of 400 to 600 °C, more preferably 450 to 550 °C to produce Black-WO 3 (BW) catalyst. manufactures. If heat treatment is performed at a temperature range of 300°C to less than 400°C, oxygen vacancy formation occurs weakly, and if heat treatment is performed below 300°C, oxygen vacancy formation does not occur and the color of the catalyst remains the same. The heat treatment was performed under various conditions and the firing time was 10 to 120 minutes, preferably 10 to 60 minutes, and more preferably 45 to 60 minutes.
  • the degree to which oxygen vacancies are activated on the surface of the catalyst varies. The longer the firing time is, the more oxygen vacancies appear on the catalyst surface. However, optimization of the calcination maintenance time is necessary to ensure high performance of catalysts activated with oxygen vacancies. High performance is achieved when the existing catalyst and oxygen vacancies on the surface are in an appropriate ratio. If the firing maintenance time exceeds 120 minutes, oxygen vacancies are strongly formed and the color of the catalyst becomes closer to black, but this is not a condition for excellent carbon monoxide removal performance. In addition, even if oxygen vacancies are weakly formed with a firing holding time of less than 10 minutes, the carbon monoxide removal performance is low.
  • the powder mixed with agate oil by adding a reducing agent to titanium dioxide is placed in an alumina crucible and heat-treated in an Ar atmosphere, preferably in a 100% Ar atmosphere, at a temperature range of 200 to 400 °C, preferably 250 to 350 °C, to obtain black- TiO 2 (BT) catalyst is prepared.
  • the reducing agent of the present invention can be calcium hydride or sodium borohydride, but calcium hydride has the disadvantage of having a long calcination time, so sodium borohydride is most preferable.
  • Heat treatment conditions were set between 10 and 120 minutes, preferably 10 to 60 minutes, and most preferably 45 to 60 minutes. After heat treatment, BT was washed with purified water and ethanol.
  • a composite photocatalyst is formed by combining BT and BW catalysts.
  • the T:W ratio of the composite photocatalyst is 10:0 to 0:10, preferably 1:1 to 19:1, more preferably 1:1 to 9:1, and most preferably 9:1. .
  • the composite photocatalyst is filtered through filter paper to produce a filter, and dried in a dryer for 12 to 24 hours, preferably 12 to 18 hours, preferably 12 to 16 hours, most preferably 12 hours.
  • the filter paper may be made of ceramic, paper, carbon, polymer, fiber, etc.
  • an air purifying filter manufactured according to a method of manufacturing a composite photocatalytic filter activated with oxygen vacancies is provided.
  • the thickness of the manufactured filter is 0.25 mm to 27 mm, preferably 0.25 mm to 20 mm, and more preferably 1 mm to 5 mm.
  • CO was removed as CO was converted to CO 2 depending on the T:W ratio of the photocatalyst included in the air purification filter.
  • CO removal rate can be optimized depending on the T:W ratio.
  • Tungsten oxide and titanium dioxide were mixed in 50 mL of purified water at a constant mass ratio of 50 mg and stirred for 30 minutes.
  • a filter was manufactured by filtering the stirred solution through filter paper (0.45 uM) using a vacuum pump. The manufactured filter was dried in a dryer for more than 12 hours.
  • Tungsten oxide and titanium dioxide were added to 50 mL at a constant mass ratio of 50 mg, and zeolite (1, 5, 10 wt%) was added and stirred together for 30 minutes.
  • the zeolite used here is Zeolite Y (Hydrogen), and it was heat treated at 110°C for 12 hours as a zeolite pretreatment process.
  • a filter was manufactured by filtering the stirred solution through filter paper (0.45 uM) using a vacuum pump.
  • a carbon nanotube filter was produced using multi-walled carbon nanotubes (MWCNT).
  • MWCNT multi-walled carbon nanotubes
  • Carbon nanotubes which are mainly hydrophobic, were modified to be hydrophilic through surface treatment.
  • aqua regia 100 mL
  • nitric acid and hydrochloric acid in a ratio of 1:3, 0.5 g of carbon nanotubes were added and stirred for 6 hours.
  • the stirred carbon nanotubes were washed several times with water.
  • the modified carbon nanotubes were dried in an oven at 60 degrees for more than 12 hours.
  • the change in catalyst color was observed after surface modification of the catalyst. Additionally, in order to determine the light absorption range of the catalyst, it was measured using an analysis device from Shimadzu. Using BaSO4 (Barium sulfate), we first set a standard and measured the light absorption spectrum in the wavelength range from 200 nm to 900 nm in the form of catalyst powder.
  • BaSO4 Barium sulfate
  • T, W, BT, and BW sample powders were measured using a field emission transmission electron microscope FE-TEM (200kV) for micro-area image observation and component and structure analysis of the ultra-fine areas of the samples.
  • Cu-K ⁇ radiation 40 kV, 30 mA
  • a wavelength of 1.5406 ⁇ was applied using PANalytical's EMPUREAN equipment to measure T, W, BT, and BW in powder form.
  • Al-K ⁇ (1486.6 eV) was applied using ThermoFisher (NEXSA) equipment to measure T, W, BT, and BW in powder form.
  • NEXSA ThermoFisher
  • the composite photocatalyst filter prepared above was used with an area of 2.5 x 2.5 cm 2 .
  • an experiment was conducted to oxidize carbon monoxide, a harmful indoor gas, to carbon dioxide. Before proceeding with the experiment, air was purged while exposed to light for 1 hour to remove carbon attached to the surface of the filter. 0.1% carbon monoxide (CO) and 21% oxygen (O 2 ) were used in a nitrogen atmosphere.
  • MFC flow controller
  • the reactor was allowed to flow for 30 minutes, and then both sides were blocked and sunlight was applied.
  • the gas in the reactor was sampled at a certain time to confirm the reduction of carbon monoxide and the production of carbon dioxide.
  • the decomposition and production amount of the gas was confirmed by quantifying carbon monoxide and carbon dioxide using GC-FID.
  • TA/W-1 and TA/W-1 Two types of composite photocatalysts, TA/W-1 and TA/W-1, were manufactured by bonding Al 2 O 3 to TiO 2 . At this time, the concentration of Al 2 O 3 is 0.05 to 0.1 M for TA/W-1 and 0.28 to 0.32 M for TA/W-2.
  • Figure 1 shows catalyst changes as the firing maintenance period increases according to an embodiment of the present invention.
  • the color of samples of tungsten oxide (BW) and titanium dioxide (BT) activated with oxygen vacancies changed.
  • BW tungsten oxide
  • BT titanium dioxide
  • the color of the sample tended to become darker, and both BW and BT changed to navy blue or black.
  • BT-1 and BW-1 were fired for 10 minutes
  • BT-2 and BW-2 were fired for 50 minutes
  • BT-3 and BW-3 were fired for 120 minutes.
  • Figure 2 shows the light absorption wavelength range and catalyst color change of tungsten oxide and titanium dioxide improved with oxygen vacancies according to an embodiment of the present invention.
  • the existing W and T exhibit strong absorption in the UV region, and the samples activated with oxygen vacancies have an expanded wavelength range of light that can be absorbed.
  • the catalysts activated with oxygen vacancies had a narrower band gap and were able to absorb light even in the visible light region.
  • Figure 3 shows TEM images of tungsten oxide (W), titanium dioxide (T), tungsten oxide (BW) activated with oxygen vacancies, and titanium dioxide (BT) catalysts according to an embodiment of the present invention.
  • (a) is tungsten oxide (W)
  • (b) is titanium dioxide (T)
  • (c) is tungsten oxide (BW) activated with oxygen vacancies
  • (d) is activated with oxygen vacancies.
  • a titanium dioxide (BT) catalyst tungsten oxides appeared to have a particle size within about 200 nm, and titanium dioxide appeared to have a particle size within about 50 nm, and there was no change in particle size and shape of the catalysts developed by firing. There was no change in the crystal structure of titanium dioxide before and after treatment, but a new crystalline phase of WO 2.92 was seen in tungsten oxide after treatment.
  • Figure 4 shows XRD of tungsten oxide (W), titanium dioxide (T), tungsten oxide (BW) activated with oxygen vacancies, and titanium dioxide (BT) catalysts according to an embodiment of the present invention.
  • W tungsten oxide
  • T titanium dioxide
  • BW tungsten oxide
  • BT titanium dioxide
  • FIG. 5 shows O 1s
  • Figure 6 shows W 4f, Ti 2p It was done.
  • the O 1s binding energy of BT has moved to a lower energy side compared to T, which means that the Ti-O peak has moved to a lower energy side and treatment to create oxygen vacancies has resulted in the formation of hydroxyl on the surface of BT. This is because the peak of Ti-OH was generated as the group was formed.
  • BW moved to higher energy than W.
  • the Ti 2p binding energy shifted to a lower energy for BT compared to T, which is a phenomenon seen as the formation of Ti +3 in BT.
  • Figure 7 shows a comparison of the removal performance of tungsten oxide (W), titanium dioxide (T), tungsten oxide (BW) activated with oxygen vacancies, and titanium dioxide (BT) catalysts according to an embodiment of the present invention.
  • Figure 7 (a) compares the carbon monoxide removal performance of T and BT
  • Figure 7 (b) compares the carbon monoxide removal performance of W and BW, comparing the existing catalysts (T and W )
  • the results were as follows. Compared to the existing catalyst, the optical performance of the developed catalyst was improved.
  • BT-2 increased the carbon monoxide removal reaction rate by about 5 times compared to T. Additionally, performance also differed depending on the catalyst treated with different firing holding times. It was confirmed that the improved optical performance of the catalyst activated by oxygen vacancies had a more efficient effect for air purification, such as carbon monoxide removal, compared to existing catalysts.
  • BT-2 and BW-2 which had relatively excellent performance, were determined, and composite photocatalysts of T, W, BT, and BW were manufactured and performance evaluated.
  • a synergistic effect was seen when two types of catalysts were combined and combined rather than single material T and W catalysts.
  • two catalysts were tested and compared under various ratio conditions.
  • Figure 8 shows a comparison of performance by ratio of tungsten oxide (W), titanium dioxide (T), tungsten oxide (BW) activated with oxygen vacancies, and titanium dioxide (BT) catalysts according to an embodiment of the present invention. Referring to Figure 8, when overall T is 90% and W is 10% (TW90 in (a), BT/W90 in (b), T/BW90 in (c), BT/BW90 in (d)), showed the best performance.
  • Figure 9 shows a comparison of the carbon monoxide removal performance of tungsten oxide (W), titanium dioxide (T), tungsten oxide (BW) activated with oxygen vacancies, and titanium dioxide (BT) catalysts according to an embodiment of the present invention and the carbon monoxide oxidation
  • the carbon dioxide production rate is shown
  • Figure 10 shows the removal of carbon monoxide by tungsten oxide (W), titanium dioxide (T), tungsten oxide (BW) activated with oxygen vacancies, and titanium dioxide (BT) catalysts according to an embodiment of the present invention. This shows a comparison of reaction speeds.
  • the performance when BT and BW catalysts are bonded together has improved, especially carbon monoxide removal of the T/BW composite photocatalyst filter.
  • the reaction speed was improved by about 8 times more than T and about 2 times compared to TW.
  • Figure 11 shows the light absorption wavelength region of the composite photocatalyst according to an embodiment of the present invention.
  • the intensity of the absorption zone was also different for each catalyst. Performance was improved due to complexation with a catalyst activated by oxygen vacancies, and the following catalysts were found to be effective for air purification, such as removal of carbon monoxide, a harmful indoor gas.
  • the optimized composite photocatalyst (T/BW) was selected, a certain amount of zeolite (1, 5, and 10 wt%) was added, and a carbon monoxide experiment was conducted under the same conditions.
  • Figure 13 shows the carbon monoxide removal and carbon dioxide production rate of the composite photocatalyst containing zeolite according to an embodiment of the present invention
  • Figure 14 shows the carbon monoxide removal reaction rate of the composite photocatalyst containing zeolite according to an embodiment of the present invention. This shows a comparison. Referring to Figure 13, the removal performance rate decreased compared to when zeolite was not included, but as the amount of zeolite increased, the carbon dioxide production rate increased.
  • zeolite has excellent adsorption power as a representative feature, and due to this feature, there is a possibility that carbon monoxide and carbon dioxide are adsorbed while purging gas in the early stages of the experiment.
  • the removal reaction rate was similar when the zeolite content was 1, 5, and 10 wt%, but was higher by about 0.07 k (h -1 ) at 5 wt%.
  • FIG. 15 shows a comparison of carbon monoxide removal reaction rates of a composite photocatalyst containing zeolite according to an embodiment of the present invention. Referring to (a) of FIG. 15, carbon monoxide was consistently removed linearly rather than non-linearly. Referring to (b) of FIG. 15, the carbon dioxide production rate increased as carbon monoxide was removed. A characteristic of carbon nanotubes is their gas adsorption capacity, so a higher carbon dioxide production rate can be observed compared to carbon monoxide removal compared to when carbon nanotubes are not used.
  • Figure 16 shows a comparison of carbon monoxide removal reaction rates of composite photocatalyst carbon nanotube filters according to an embodiment of the present invention. Referring to FIG. 16, even when a carbon nanotube filter is used, the catalyst's optical activity is outstanding and the carbon monoxide removal performance shows a removal efficiency of over 80% and a reaction rate of about 0.6 k (h -1 ) in 3 hours.
  • FIG. 17 shows the carbon monoxide removal rate of the TAW composite photocatalytic filter according to a comparative example of the present invention. Referring to FIG. 17, the performance of each prepared TA/W catalyst was significantly lower than that of TW or T/BW described in this study, with about 20-25% of carbon monoxide removed.

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Abstract

La présente invention concerne un procédé de fabrication d'un filtre photocatalyseur composite activé par lacunes d'oxygène, le procédé comprenant : une première étape de préparation d'un catalyseur de WO3 noir (BW) par traitement thermique d'une poudre d'oxyde de tungstène sous une atmosphère de gaz réducteur, dans une plage de température de 400 à 600 °C ; une deuxième étape de préparation d'un catalyseur de TiO2 noir (BT) par traitement thermique d'un mélange de dioxyde de titane et d'un agent réducteur sous une atmosphère de gaz inerte, dans une plage de température de 200 à 400 °C ; une troisième étape de formation d'un photocatalyseur composite par combinaison des catalyseurs BT et BW préparés ; et une quatrième étape d'incorporation du photocatalyseur composite dans du papier filtre pour fabriquer un filtre, le monoxyde de carbone étant éliminé de l'environnement ambiant par adsorption sur le filtre lorsque le rapport T : W du photocatalyseur composite est compris entre 1 : 1 et 19 : 1.
PCT/KR2023/013184 2022-09-05 2023-09-04 Procédé de fabrication de filtre de photocatalyseur composite activé par lacune d'oxygène, et filtre associé de purification d'air WO2024053969A1 (fr)

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KR1020220111808A KR20240033732A (ko) 2022-09-05 2022-09-05 산소 빈자리로 활성화된 복합 광촉매 필터의 제조방법 및 이에 따른 공기정화필터

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KR101798129B1 (ko) * 2016-07-25 2017-11-15 재단법인대구경북과학기술원 금속산화물의 환원방법 및 이를 이용한 환원된 타이타니아의 제조방법

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KR101768705B1 (ko) * 2016-02-29 2017-08-17 동국대학교 산학협력단 광촉매를 이용한 그린인프라 및 이에 사용되는 여재층
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