The present application is a continuation of, and claims priority to, PCT/CN2015/080352, filed on May 29, 2015, the disclosure of which is hereby incorporated by reference in its entirety.
Nano-sized metal oxide materials, such as titanium dioxide (TiO2), can be applied to the surface of a substrate forming a particle film and used as photocatalysts. Photocatalysts can be applied in many areas, including food, pharmaceutical, and cosmetics industries. For example, under UV rays, a TiO2 photocatalyst can have a strong catalytic degradation effect, and can effectively degrade toxic or harmful gases in the air, kill a variety of bacteria, and break down or detoxicate toxins released by the bacteria or fungi. In addition, photocatalysts can also be used as deodorants or anti-contaminants.
Photocatalysts typically utilize oxygen and water molecules in the air to catalyze the conversion of organic compounds that the photocatalysts come into contact with into carbon dioxide and water. During this process, the photocatalysts remain unchanged while catalyzing the chemical reactions, thereby having a long effectiveness and incurring low maintenance cost. Meanwhile, titanium dioxide itself is nontoxic, and has been widely used in food, pharmaceutical, and cosmetics industries.
The present disclosure relates to photocatalyst apparatuses comprising fine-array porous materials, and to their practical applications.
Some embodiments disclosed herein provide photocatalyst apparatuses comprising high surface-area-to-volume ratio fine-array porous films with a surface area larger than 100 cm2, such as 20 cm×20 cm. In some embodiments, the photocatalyst apparatuses comprise a large bulk fine-array porous material with a three-dimensional (3D) structure.
The sizes of the pores of the fine-array porous films or fine-array porous materials with 3D structure can be, for example, about 100nm -5 mm. Meanwhile, the pores in these materials have substantially uniform sizes, with a variation of <20%, or of <10% according to some embodiments. These features are in contrast with the porous materials manufactured by existing approaches. For example, existing metal foams typically have a pore size of >500 μm, and a specific surface-area of about 14˜3100/mm, with large pore size variations (such as >100%).
The fine-array porous materials according to some embodiments possess features of photonic crystals, and thus can reflect light with specific wavelengths. For example, the fine-array porous materials according to some embodiments of the photocatalyst apparatus can efficiently reflect the UV light (such as through total reflection) emitted by the optical pump, a feature that allows efficient illumination of activating light by the photocatalyst apparatus, thereby significantly elevating the photocatalytic activity of the photocatalyst apparatus and additionally reducing the damage to living organisms caused by the UV light.
Existing photocatalysts typically take the form of nano-sized powders, which generally need a binder to tightly adhere the nanoparticles together and on the surface of a porous carrier. Use of the adhesive binder can substantially reduce the working specific surface area of a photocatalyst, thereby significantly reducing the efficiency of the catalytic conversion. Therefore, to achieve standard values required for a catalytic reaction. more of the photocatalyst material may be needed. In addition, a photocatalyst may need to be irradiated with UV light to function properly. UV light has a relatively high energy, and may result in deterioration of some materials, or cause pathological changes to cells of living organisms. Existing photocatalysts often need porous carriers, whose specific surface area can determine the amount of the photocatalyst it carries, and the ability to catalyze the reaction.
Photocatalysts can use a metal foam as a carrier.
Embodiments disclosed herein provide a fine-array porous material/film that can be used as carrier for photocatalysts in a photocatalyst apparatus or system.
Porous materials, such as metal foams and fine-array porous materials as disclosed herein, can have high surface-area-to-volume ratios, which can be described as:
where Sv is the specific surface area, d is the average pore diameter in units of mm, θ is the porous ratio. For example: for a d=0.01 mm, a porous ratio of 90%, the specific surface area is 2425/mm.
Table 1 below compares parameters, as defined in association with Equation (1), of conventional metal forms with those of the fine-array porous materials disclosed herein. As shown, the specific surface areas of the fine-array porous materials can be higher than 3130/mm, such as higher than 4100/mm. However, specific surface areas of the fine-array porous materials can also be in the range of 10/mm and 3130/mm, and would still have superb properties for various applications resulting from other properties unmatched by metal forms. For example, fine-array porous materials according to some embodiments, with a specific surface area >10/mm, can have substantially uniform pore sizes, such as of <20% as measured by the standard deviation, or of <10% as measured by the standard deviation.
In contrast to conventional metal foams that have relatively low specific surface areas and lack of uniformity in pore sizes, the fine-array porous material has larger specific areas, and the pores therein are also highly uniform.
Some embodiments of the fine-array porous film, as illustrated by
Disclosed herein also include photocatalyst apparatuses or systems comprising fine-array porous films/materials.
In some embodiments, as illustrated in
In the embodiment as shown in
In some embodiments, as illustrated in
In some embodiments, as illustrated in
As a result of the very high specific surface area of the fine-array porous photocatalyst members 520 and 620 according to the embodiments as illustrated in
In addition, by controlling the composition of the photocatalysts 424, 524 or 622, and the pore size of the fine-array porous film 422, 522 or 622 in the photocatalyst member 420, 520 or 620, in the embodiments as illustrated in
For light illuminating vertically (90°) to a fine-array porous film, the light reflecting property of a film can be described by the corrected Bragg's equation:
λc=2neff×d, (2)
n
eff
=[n
air
2
×f+n
material
2×(1−f)]1/2, (3)
wherein λc is the wavelength of light being reflected, neff is the effective refractive index, d is the distance between neighboring pores of the fine array. nair and nmaterial are the refractive indices of air and a porous material, respectively; f is the volume factor of the air bubble in the fine-array porous material; d=(2/3)1/2D wherein D is the diameter of the air bubble.
Table 2 below summarize the parameters of three compositions used in the fine-array porous film for the photocatalyst apparatus according to some embodiments. According to Table 2, if a fine-array porous film is made from TiO2 is used, using nTiO2=2.50 and nair=1, f=0.74, and for an UV wavelength λc=365 nm, it can be calculated that D=190 nm.
The bandgap (Eg) of TiO2/ZnO is about 3.2 eV, corresponding to a wavelength of about 1240/3.2=385 nm. Therefore, TiO2 or ZnO can absorb light with wavelengths less that 385 nm, activating the photocatalyst effects. Similarly, Cu2O has an Eg of about 2.1 eV, corresponding to a wavelength of about 1240/2.1=590 nm. Therefore, Cu2Ocan absorb almost all light with wavelengths <590 nm, activating the photocatalyst effects. Other direct-band-gap materials such as MnO, Mn2O, RuO2, etc. can also have the photocatalyst effects, with their different Eg's determining the pore sizes of the fine-array porous materials.
The photocatalyst member 720 comprises a fine-array porous film carrying photocatalysts, and can take the form of one of the embodiments 420, 520 and 620 as illustrated in
The photocatalyst apparatus disclosed herein can find many applications. In one application, a photocatalyst apparatus can be installed in a refrigerator to help keep the food fresh as well as to provide lighting. This apparatus may avoid food degradation or pathological degradation of cells/nutrients under the UV light.
In another application, a photocatalyst apparatus can be used to keep flowers fresh while avoiding damaging the flowers with direct UV light.
In yet another application, a photocatalyst apparatus can be used for indoor or outdoor lighting. The photocatalyst apparatus, if used as part of an outer shell, a substrate, or a heat dissipater of a lighting device and designed to be able to utilize visible light in the photocatalysis reaction, can have advantages of facilitating air circulation and having optimal catalytic activities because of the high specific surface area of the fine-array porous film.
In yet another application, a photocatalyst apparatus can be used in a plant culturing facility, which can facilitate plant growth by providing light to plants and by effectively killing harmful bacteria and fungi.
In yet another application, a photocatalyst apparatus can be used as lighting in hospital or general indoor sanitation. The UV light pump photocatalysts can kill bacteria while human body exposure to the UV light can be reduced. For example, the UV light pump can kill germs by not only the reactive oxygen species, but also by stimulating lethal mutations in the germs. The apparatus can have air flowing there through while killing the germs in the air, with little or no UV leakage to the environment as the result of total reflection of the photonics crystal properties. In some other embodiments, non-UV light is employed as the light pump, without needing the direct germicidal properties of UV light.
In some applications, the photocatalysts used can be optically pumped by visible light. In some implementations, the photocatalysts optically pumped by visible light can be used as a part of an LED lighting apparatus for bactericidal and/or deodorant functions. For example, the fine-array porous film carrying photocatalysts can be disposed at a heat sink of the LED lighting apparatus (such as an LED lamp), and can have bactericidal/deodorant/heat-dissipating functions.
In some embodiments, an apparatus employing a fine-array porous film carrying a photocatalyst can be used in an air filtration/purification apparatus. The photocatalytically active fine-array porous film can filter out the dust and pollutants from the air. At the same time, the photocatalysts add bactericidal/deodorant functions to the air filtration apparatus.
In some embodiments, an apparatus employing a fine-array porous film carrying a photocatalyst can be used in a water filtration/purification apparatus. Under the sunlight, the photocatalytically active fine-array porous film can filter out the dust and pollutants from the water, and have bactericidal/decontamination functions. Additionally, if combined with LED lights, such apparatus can be used in fish farms to provide lighting as well as stabilize pH and water quality; the apparatus can photocatalytically remove nitrates and amines that are generated by fish in the water.
Advantages of one or more embodiments disclosed herein may include one or more of the following. (1) The fine array porous film has a specific surface area much larger than metal forms and other carriers, and thus is a far superior carrier with significantly catalytic capability when used as a carrier for photocatalysts. (2) The fine array porous film has properties of photonic crystals, and can reflect light of specific wavelengths, thereby significantly improving the probability for photons to interact with the photocatalysts. (3) Compared with metal foams, using the fine array porous film as the carrier can reduce the UV light leakage (the portion that has not interacted with the photocatalysts), thereby reducing the chance for pathological degradations of biological cells under the UV light. (4) When implemented at the visible light wavelength range, the fine array porous film carrying the photocatalysts can be part of LED lighting devices for use as a lighting system capable of disinfection and decontamination, or act as a deodorant.
A fabrication system according to some embodiments disclosed herein can fabricate the suitable fine array porous film. The system can include a colloidal particle template formation portion configured to fabricate a colloidal particle template; an infiltration portion configured to infiltrate the colloidal particle template with an infiltrant substance; and a template removal portion configured to remove the colloidal crystal template and keep the infiltrant substance substantially intact.
A process flow of manufacturing a fine-array porous material according to some embodiments may include: (i) surface-charged particle deposition forming an array (assembly process), (ii) deposition/infiltration, and (iii) template removal. The system can include portions (e.g., modules) to respectively realize these steps. A movable conductive tape can be used to transport the colloidal particle template between the waterproof inlet and outlet of each tank.
More specifically, the following steps may be included.
(1) An electrophoresis solution containing a monodispersed colloidal nanosphere suspension can be disposed in an electrophoresis tank. A working electrode can comprise a movable continuous conductive tape configured to feed into the electrophoresis tank, provide a surface for the formation of a colloidal particle template in the electrophoresis tank, move out of the electrophoresis tank if the electrophoresis self-assembly of the colloidal particle template is complete. The working electrode can be fed at a variable rate. In some embodiments, the working electrode can be a solid, such as a metal plate, a silicon wafer, ITO glass, etc.
(2) The colloidal particle template can be transported, for example using the conductive tape or other substrate, through the oven for drying. The drying process can be performed while the template is moving (i.e., dynamic), or while the template is static inside the oven.
(3) The working electrode (e.g., tape) that comes from the electrophoresis portion carrying the dried colloidal particle template can be fed into a deposition tank for plating (such as electroplating, Sol-Gel, CVD, PVD, etc.). Using the fine array of uniformly stacked particles as a template, metal, polymers, ceramic or other materials can be plated over the template filling the space between the particles, forming a fine-array porous film over the colloidal particle template.
(4) An etching solution can be employed for removal of the colloidal particle template, and the fine-array porous film can therefore be obtained. An example of a fine-array porous film with a high specific surface area is illustrated in
The fine-array porous film can be designed in the fabrication process with specific porous sizes and materials, such that it has specified optical characteristics such as reflecting/absorbing light of specific wavelengths, as described above with respect to Table 2.
One or more photocatalysts can be disposed over a sidewall or surface of the fine-array porous film.
The photocatalysts can percolate into the pores, allowing for a higher probability for them to interact with light. In some embodiments, a transparent material is used to form the fine-array porous film, such that at least some light can transmit therethrough for lighting. In some other embodiments, the fine-array porous film is designed to absorb light of specified wavelengths to increase activation of the photocatalysts. In contrast to conventional metal foams that have relatively low specific surface areas and lack of uniformity in pore sizes, the fine-array porous material has larger specific areas, and the pores therein are also highly uniform.
As a result of the designs of the pore sizes and the thickness of the fine-array porous film, the film selectively reflects and/or absorb light of specific wavelengths (such as UV), and the reflected light can further react with the photocatalysts, thereby improving the overall reaction probability between photons and the photocatalysts.
The substrate can be removed from the fine-array porous film comprising tightly stacked pores, and the resulting film can have a large area. The resulting film can also be flexible, allowing the system to take many different and/or flexible shapes.
The fine-array porous film can be cut to obtain films or specified shapes and sizes for various applications.
In some embodiments, the colloidal particle template formed by the assembly process can be made of polystyrene (PS), SiO2, PMMA (Poly(methyl methacrylate)), or any powder substance with a sphere shape, with a particle size in the range of about 100 nm-5 mm and diameter variation (e.g., standard deviation) within about ±20%, optimally within about ±10%. For example, in an embodiment, the particle size is about 200 nm±40 nm; in another example, the particle size is about 300 nm±60 nm. The particles can have spherical shapes, and can be hollow or solid spheres. In some other embodiments, non-spherical shapes can be employed.
During the fabrication process, according to some embodiments, procedures are taken to avoid the photocatalyst particles being covered by a binding material. In some embodiments, the LED chip can be packaged first with a transparent silicone for protection, and the photocatalyst particles can then be disposed over the packaging, and can receive the pumping light while being in contact with air.
The LED substrates can be flexible, porous, or solid. The fine-array porous film can be soaked with the catalysts and then dried, and subsequently bonded to the substrate.
In addition to the photocatalyst apparatuses and systems as disclosed herein, a fine-array porous material may be employed as carriers for other chemical catalysts in other practical applications, because its significantly large specific surface area make it ideal for use as a catalyst carrier for optimized catalysis. In one embodiment, an automotive three-way catalytic converter may comprise a fine-array porous material carrying three-way catalysts, comprising at least one of platinum, palladium and rhodium, having an improved performance in simultaneous reduction of nitrogen oxides and oxidation of carbon monoxide and unburnt hydrocarbons, and thereby achieving a better vehicle emission control. In another embodiment, a fuel cell may comprise a fine-array porous material carrying appropriate catalysts, such as platinum and nickel, at its anodes and/or cathodes to allow optimized chemical reactions occurring therein. In yet another embodiment, a fine-array porous material carrying some acid catalysts, such as aluminum oxide and aluminosilicate, may be used in petrochemical industry, for instance in fluid catalytic cracking and hydrocracking.
Although specific embodiments have been described above in detail, the description is merely for purposes of illustration. It should be appreciated, therefore, that many aspects described above are not intended as required or essential elements unless explicitly stated otherwise. Various modifications of, and equivalent acts corresponding to, the disclosed aspects of the exemplary embodiments, in addition to those described above, can be made by a person of ordinary skill in the art, having the benefit of the present disclosure, without departing from the spirit and scope of the disclosure defined in the following claims, the scope of which is to be accorded the broadest interpretation so as to encompass such modifications and equivalent structures.
Number | Date | Country | |
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Parent | PCT/CN2015/080352 | May 2015 | US |
Child | 15607567 | US |