Photocatalytic panel and system for recovering output products thereof

A system and method is provided for using sunlight to convert an atmospheric gas to an output product and capture that output product. A photocatalytic element is encapsulated within a chamber in which the chamber is light transmissive, and is substantially permeable to the atmospheric gas and substantially impermeable to the output product. The photocatalytic element may be composed of a photocatalytic composition, comprising a first constituent capable of capturing or binding an atmospheric gas, a second constituent capable of reducing the atmospheric gas using energy from the sunlight, and a third constituent adapted to absorb sunlight, all combined into a single polymer. A fourth constituent may be added that is hydrophobic or hydrophilic depending upon the nature of the other three combined constituents.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is related to commonly-assigned co-pending application Ser. No. 13/176,523, filed on Jul. 5, 2011, titled “Photocatalytic Panel and System for Recovering Output Products Thereof”, and to commonly-assigned co-pending application Ser. No. 13/176,582, filed on Jul. 5, 2011, titled “Environmentally Responsive Building and Control System Therefor.” The entire disclosure of each of these two applications is incorporated herein by reference to the extent permitted by law.

FIELD OF THE INVENTION

The embodiments disclosed herein relate to devices and methods for using sunlight and atmospheric gases to generate useful output products. In particular, the embodiments incorporate elements for achieving photocatalysis or photosynthesis into panels, along with systems for extracting and storing the output products.

BACKGROUND

The concern over greenhouse gases and their effect on the atmosphere and global ecosystem has grown over the last decade. Greater awareness of the effect of certain gases, such as carbon dioxide (CO2), has prompted efforts to reduce carbon emissions. As a result, many regulated industries incorporate local systems for scrubbing emissions to reduce the amount of CO2and other greenhouse gases discharged into the atmosphere. Fossil fuel powered vehicles include catalytic converters to reduce harmful exhaust emissions.

However, cost and performance concerns have hampered compliance or even acceptance of systems to reduce greenhouse gas emissions, especially in growing industrial economies. In some cases the greenhouse gases can be recycled and re-used in combustion. However, many of the current approaches to minimizing greenhouse gas emissions simply convert the harmful component of the gases into an output that can be disposed of in a landfill.

As concern over greenhouse gases, and especially CO2, increases alternative solutions become more critical, particularly solutions that do not require government-mandated and regulated compliance. An optimal solution would be to reduce greenhouse gases while generating a useful product that does not require some other form of disposal.

SUMMARY

In one aspect, a photocatalytic panel is provided comprising a housing having a plurality of walls defining a chamber and an outlet in communication with the chamber. At least one wall of the housing has a portion that is transmissive to sunlight. A photo-conversion element is disposed within the chamber for exposure to sunlight through the transmissive portion. The photo-conversion element is operable to use sunlight to convert an atmospheric gas into an output product dischargeable through the outlet. At least one of the plurality of walls includes a permeable portion having a high permeability to the atmospheric gas and a low permeability to the output product.

In a further aspect, a photocatalytic composition is provided that comprises a first constituent or composition (A) capable of capturing or binding an atmospheric gas, a second constituent or composition (B) capable of reducing the atmospheric gas using energy from the sunlight, and a third constituent or composition (C) adapted to absorb sunlight. The constituents may be monomers that are combined in a suitable manner to form a single polymer. In one feature, the monomers are combined in a repeating chain with spacing between adjacent monomers on the nanometer scale. The repeating chain may be configured so that the monomer capable of reducing the atmospheric gas (monomer B) is immediately adjacent both the supply of atmospheric gas, namely monomer A, and the source of energy, namely monomer C. The photocatalytic composition may further include a fourth constituent that is hydrophobic or hydrophilic depending upon the hydrophilic/hydrophobic nature of the other constituents.

DETAILED DESCRIPTION

Referring toFIG. 1, a photocatalytic panel10is provided that includes a housing12defining a chamber14. The housing12may be configured for the panel10to serve as a building panel. The housing may thus have sufficient structural integrity to act as the “skin” of the building. Alternatively, the housing of the panel10may be configured as a “stand-alone” element. The chamber14is preferably substantially sealed or encapsulated to avoid the loss of gas of volatile products within the chamber.

A photo-conversion element16is disposed within the chamber14, in which the conversion element is operable to convert sunlight and atmospheric gas(es) into an output product. The photo-conversion element may include a composition capable of achieving photosynthesis or “artificial photosynthesis” in which air, water and sunlight are processed to produce an output product, much like a biological plant. In another form, the photo-conversion element16is a photocatalytic panel operable when “powered” by sunlight to react with carbon dioxide (CO2) in the presence of water to produce an output product such as methanol, carbon monoxide or certain hydrocarbons. In one example, this reaction can be accomplished with a photocatalytic element containing titanium dioxide (TiO2) nanoparticles. The TiO2nanoparticles may be augmented with carbon nanotubes or other metallic nanoparticles to improve the reaction efficiency. For the purposes of the present disclosure, the photo-conversion element will be referred to as a photocatalytic element16, with the understanding that the element may operate by “artificial photosynthesis” to produce different output products.

The photocatalytic element16may be supported on a generally rigid substrate18capable of supporting the photocatalytic element within the chamber14. The substrate may be formed of a sufficiently rigid material that may be inert to the reaction components and reaction products of the photocatalytic or photosynthesis reaction. In certain embodiments, the substrate and the housing may be formed of the same material, which may be a metal, polymer, glass or even a ceramic. The photocatalytic element may be associated with the substrate in any manner, such as by applying the photocatalytic element as a layer on the substrate or by affixing a separately formed photocatalytic sheet on the substrate.

At least one of the walls12aof the housing is configured to allow sunlight to pass through and onto the photocatalytic element. The wall12ais thus provided with a portion that is light transmissive, or more particularly transmissive to light wavelengths favorable to the photosynthesis reaction. The wall12amay further include a portion that is permeable to an atmospheric gas or gases that are necessary for the photosynthesis reaction. For instance, the portion of the wall may be highly permeable to CO2. Moreover the wall portion is impermeable or has a low permeability for reaction products of the photosynthesis reaction. Thus, in embodiments in which the reaction product is methanol, the portion of wall12ais generally impermeable to methanol so that this output product will not leak from the chamber14.

In one embodiment, the wall12ais provided with a membrane20spanning all or a portion of the wall, as depicted inFIG. 1. The membrane is formed of a material that is permeable to atmospheric gas, such as CO2, impermeable to the reaction product, such as methanol, and light transmissive. In certain embodiments the membrane maybe formed of polysiloxane, polyamine, polyphenylene-oxide, cellulose-acetate, ethylcellulose, polyethylene, polypropylene, polybutadiene, polyisoprene, polystyrol, polyvinyl, polyester, polyimide, polyamide, polycarbonate, or other similar polymeric materials.

Certain photocatalytic and photosynthesis reactions require water, so the photocatalytic panel10is configured to direct water to the photocatalytic element16. In one embodiment, the housing12includes a portion that is configured for passage of atmospheric moisture into the chamber14. Thus, the membrane20may also be permeable to atmospheric moisture. Alternatively, a photocatalytic panel30may be provided that includes one portion32that is permeable to the atmospheric gas and another portion34that is permeable to atmospheric moisture, as illustrated inFIG. 2. Each portion may thus incorporate a membrane having the requisite permeability, as well as an impermeability or low permeability for the photosynthesis output product(s).

The substrate18is formed of a material that is essentially inert to the photocatalytic element16and to the photosynthesis process. The material is sufficiently strong to support the photocatalytic element within the chamber, while maintaining a thin profile. In some embodiments, the photocatalytic element16is transparent or translucent. In these embodiments, the substrate18may incorporate a reflective surface onto which the photocatalytic element is disposed. The reflective surface will reflect any sunlight that passes through the layer16back into the layer to feed the photosynthesis reaction.

The housing12is provided with an outlet24for discharge of the photosynthesis output product(s). In certain embodiments the output product(s) are primarily gaseous, such as methanol, CO or certain hydrocarbons. The outlet24may thus be positioned in a variety of locations on the housing. It may be contemplated that a flow impeller, such as an exhaust fan, may be integrated into the outlet to ensure that the photosynthesis output product(s) will exit the chamber14. Alternatively, the outlet24may open to a low pressure chamber to induce gas flow across the outlet. In addition, it is contemplated that the outlet24includes a filter that is permeable to the output product(s) but substantially impermeable to the photosynthesis gas, such as CO2, as well as to water or moisture within the chamber. In some photosynthesis processes, the output product(s) may include a liquid, with the outlet24being appropriately positioned and configured for discharge of the liquid output product(s).

The photocatalytic panel10shown inFIG. 1may be modified to accept water from an external supply. Thus, the photocatalytic panel10′ shown inFIG. 3amay include a water inlet26in the housing12′, in which the inlet is connected to a water source, such as a building water supply. The water may be provided directly from the inlet26to the photocatalytic element16. The panel may be configured to distribute the water across the panel to optimize the photosynthesis reaction on the panel. Thus, the panel may be configured with water distribution channels. In one embodiment, the photocatalytic element16is provided with a capillary sheet17disposed between the panel and the substrate18. This capillary sheet is configured to transport water by capillary action throughout the entire photocatalytic element. The inlet26may incorporate a valve27between the inlet and the water source to control the flow of water into the photocatalytic panel10′. A water sensor28may be provided inside the chamber14or in contact with the photocatalytic element16to evaluate the water level of the element. The sensor may be a humidity sensor or a moisture sensor that is linked to the valve27to control the flow of water into the photocatalytic panel. Alternatively, the inlet26may provide water to a reservoir with the capillary sheet17in direct contact with the reservoir. The sheet will draw water from the reservoir as needed by capillary action. The reservoir can be configured to be replenished when the water in the reservoir drops below a predetermined level.

In another embodiment, a photocatalytic panel40may be configured to control the sunlight exposure for photocatalytic element, as depicted inFIG. 4. For certain photocatalytic elements, the compositions may degrade over time when exposed to sunlight. It is therefore desirable to limit this exposure to thereby improve the longevity of the photocatalytic element. In this embodiment, the photocatalytic panel40includes a housing42defining a chamber44. The photocatalytic element46is disposed within the chamber but in this embodiment is sized to span only a portion of the dimension of the housing. More particularly, the photocatalytic panel40is provided with a gas permeable membrane50, like the membranes discussed above, and an optical window52in direct alignment with the photocatalytic element46. The element46and window52may be generally coextensive. The photocatalytic panel40further includes a shield51that is arranged to slide across the wall42aof the housing. The shield51may thus variably block the optical window52to control the amount of sunlight passing to the photocatalytic element. The movement of the shield may be controlled in relation to the output of the photocatalytic element46and/or the availability of reactive atmospheric gas (such as CO2) within the chamber44. For instance, if the CO2level within the chamber is too low to sustain a significant photosynthetic or photocatalytic reaction, there is no need to provide sunlight to the photocatalytic element. In this instance, the shield51may be positioned to completely block sunlight to the photocatalytic element. As the CO2level increases the shield can be moved to gradually open the optical window and expose the photocatalytic element to sunlight.

In most cases, the amount of sunlight available for a photosynthesis or photocatalytic reaction exceeds the CO2available to sustain the reaction, at least within the controlled, sealed environment of the photocatalytic panels disclosed herein. Consequently, the photocatalytic panel40may be modified to increase the ability of the panel to accept CO2from the atmosphere. As shown inFIG. 5, a photocatalytic panel60may be configured similar to the panel40, with an optical window72aligned and generally coextensive with a photocatalytic element66mounted on a substrate68within the chamber64. A portion of the housing62may be configured to support multiple membranes70a,70band70cthat are permeable to CO2. More membrane surface area means more CO2passing from the atmosphere into the chamber64. This surface area may be further increased by incorporating folds into the membranes, as illustrated inFIG. 5. This “accordion” or corrugated configuration significantly increases the surface area of each membrane70a,70band70c. In some applications a single membrane with this accordion feature may be sufficient for optimal photosynthetic or photocatalytic reaction within the building panel.

In the embodiments ofFIGS. 1-5, the photocatalytic element is supported on a substrate that is mounted within the encapsulated or sealed chamber. Brackets (not shown) may be used to mount the substrate (such as substrate18) to the interior of the housing (such as housing12). In order to replace a spent photocatalytic element, the housing may be configured to permit removal of the layer and substrate. In one approach, a wall is configured to be removed from the housing to provide access to the photocatalytic element. In another approach, an opening or slot may be provided in a wall of the housing so that the layer and substrate can slide into and out of the chamber. Other methods and means for removably supporting the photocatalytic element within the sealed chamber are contemplated.

In certain embodiments, the separate substrate may be eliminated by mounting the photocatalytic element directly to a wall of the photocatalytic panel. Thus, as shown inFIG. 6, a photocatalytic panel80includes a housing82defining a sealed chamber84having an outlet94for the photosynthesis/photocatalysis output products. An exterior wall82aof the housing may be provided with an optical window92configured to be transmissive to sunlight or more particularly to light of a wavelength effective for the photosynthesis or photocatalysis reaction. In this embodiment, the photocatalytic element86is mounted directly to the optical window92. An opposite wall82bof the housing may include a membrane90or other feature that is permeable to reaction gases, such as CO2. The membrane may also be permeable to moisture, as described above, or the photocatalytic panel80may be configured to integrate with an external source of water necessary to conduct the photosynthesis/photocatalysis reaction.

In the embodiments ofFIGS. 1-6, the encapsulated photocatalytic panel is gas filled with a gaseous output product. During a photosynthesis/photocatalysis reaction the chamber (such as chamber14) will be filled with CO2allowed to pass through the membrane20and a gaseous output product such as methanol.

Alternatively, the photocatalytic reaction may occur in a liquid environment with the output product dissolved in the liquid for discharge. A photocatalytic panel100shown inFIG. 7includes a housing102defining an encapsulated or sealed chamber104. A photocatalytic element106is supported on a substrate108disposed within the chamber. One wall102aof the housing is provided with an element110that is permeable to gases for sustaining a photocatalytic reaction, such as CO2, and light transmissive. It is understood that the element may be a membrane with these properties or may be two elements supporting the two properties separately.

In this embodiment, the housing102is configured to contain a liquid, preferably a water-based solution useful for supporting a photocatalytic or photosynthesis reaction in the element106. Moreover, the liquid is preferably miscible with the output products of the photocatalytic/photosynthesis reaction. The liquid, such as water or a buffered water solution, is provided to the chamber104through inlet116and discharged via outlet114. A pump120may be provided at the outlet, as shown inFIG. 7, or at the inlet to provide a continuous flow of liquid through the photocatalytic panel100. The liquid is intimate contact with the portion of the element110that is permeable to the reaction gas, such as CO2, so that the gas can dissolve in the liquid. In one embodiment the liquid is water which is useful to support the photocatalytic or photosynthesis reaction and which is known to readily dissolve CO2. Water is also known to dissolve certain photocatalytic output products, such as methanol. The liquid flowing through the photocatalytic panel100may also physically transport other reaction products that may not dissolve in the liquid.

The outlet114of the photocatalytic panel100feeds to a separator chamber122that is operable to separate and pass the reaction products while recycling the liquid or water. The chamber122may thus include a separation element or membrane126that is configured to permit passage of the reaction products while remaining substantially impermeable to the liquid, such as water. The separated output product is discharged from the separation chamber122through outlet128for storage or transport.

The chamber122is connected to a recycle conduit129that returns the liquid/water back to the inlet116. Since a certain amount of the liquid/water is necessarily consumed during the photocatalytic/photosynthesis reaction, a refill inlet117is provided at the inlet116. The refill inlet is connected to a liquid/water supply and may be regulated with a control valve configured to ensure that the chamber104of the building panel100is filled but not over-pressurized.

In another embodiment, a photocatalytic panel130shown inFIG. 8includes a photocatalytic element136that is configured for enhanced catalytic reaction by the application of a voltage to the element. The photocatalytic element136is mounted on a substrate138that includes an electrically conductive portion. The building panel130includes a housing132defining a chamber134within which the photocatalytic element is supported. A wall132aof the housing incorporates an element140that is permeable to CO2but impermeable to the photocatalylitic or photosynthetic output products and to a liquid, such as water, filling the chamber. As in the embodiment shown inFIG. 7, the housing defines an outlet144that may incorporate a control valve150to direct flow of water laden with the reaction output product to a separator152. The separator152has an outlet158for the separated output product and is connected to a recycle conduit160that returns the liquid/water to the inlet146to the chamber134. Additional water is provided through a refill inlet162.

In a further aspect, the photocatalytic panel130shown inFIG. 8includes means for applying a voltage to the photocatalytic element136. Thus, an electrode or electrode plate167is disposed within the chamber134offset from the photocatalytic element134and substrate138, with a conducting liquid, such as water, disposed within the gap. The electrode plate167and conductive portion of the element136and/or substrate138are connected to a voltage source165by respective electrical wires169,171. In one aspect, the voltage source may be a photovoltaic converter exposed to sunlight so that the photocatalytic panel does not need to be connected to an external power source. The photovoltaic converter165may be sized to provide power to other components of the photocatalytic panel, such as the valve150. In one specific embodiment it may be envisioned that the voltage course generates voltage in the range of 1-3V.

The photovoltaic converter165may be further sized to complement the capacity of the photocatalytic element136. Both elements (the converter and photocatalytic element) rely upon sunlight for energy input. An increase in the intensity of the sunlight increases the amount of catalytic or photosynthetic reaction in the element136. This increased reaction requires more electrical energy. As the sunlight intensity increases the output of the photovoltaic converter increases. The increased capacity/output of the photocatalytic element and photovoltaic converter can be coordinated to optimize the amount of output product generated by the photocatalytic panel.

It is known that many photocatalytic or photosynthetic materials can degrade under constant exposure to sunlight. Moreover, certain materials are susceptible to specific wavelengths in the sunlight that are not essential to support the photocatalytic or photosynthetic reaction. The photocatalytic panels disclosed herein may be configured with various filters to limit exposure of the photocatalytic elements to harmful wavelengths in the sunlight. The filter may be associated directly with the photocatalytic element or may be associated with the light transmissive portions of the housing wall.

The photocatalytic panels disclosed herein may be associated with a building or may be free-standing such as part of a solar power facility. The panels may be mounted on a building surface or may be configured to replace a non-load bearing building panel, such as a window. In the latter case, the photocatalytic panel preferably includes opposite housing walls that are light transmissive. For instance, in the photocatalytic panel10shown inFIG. 1, the wall12amay include a portion that is light transmissive, which may be the CO2permeable membrane20. The opposite wall12bmay also be formed of a light transmissive material, such as the optical window shown inFIG. 4. The photocatalytic element, such as element16and supporting substrate18, may be sized to provide a clear optical path through a portion of the building panel10.

In one example shown inFIG. 9, a photocatalytic panel, such as panel10, is mounted on a roof surface R of a building B with the panel arranged for optimum sun exposure. It is also contemplated that any photovoltaic element, such as the converter165shown inFIG. 8, could also be mounted on the same building surface in proximity to the photocatalytic panel10.

The photocatalytic panel may be part of a system for harvesting the output product of the photocatalytic or photosynthetic reaction. Thus, the outlet of the photocatalytic panel, such as outlet24, may be connected by a conduit180to a storage tank182. The nature of the conduit and tank may depend upon the nature of the output product, whether a gas or a liquid. In may be contemplated that the continuous generation of output product in the photocatalytic panel will result in an increased pressure within the photocatalytic panel that will automatically drive the output product from the photocatalytic panel down the conduit180to the storage tank182. Gravity may also assist in conveying the output product to the storage tank, especially for a liquid output product. A gaseous output product may require a regulated pump (not shown) to help draw the gas from the building panel and convey it to the storage tank182. Moreover, a pressure relief valve may be provided to prevent excessive and potentially damaging gas pressure within the building panel. The photocatalytic panel or conduit180may be provided with a pressure sensor capable of sensing the pressure within the building panel. If the internal pressure exceeds a threshold value, the sensor may activate components to stop or slow the catalytic/photosynthetic reaction. This may include moving a shield, such as shield51inFIG. 4, to block sunlight, or may include controlling the water supply to the photocatalytic panel, such as by controlling the valve27shown inFIG. 3a. Alternatively, or in addition, a temperature sensor may be provided within the chamber to control the system components in response to excessive temperature within the photocatalytic panel. In the case of the water-filled chamber, such as in the embodiment shown inFIG. 7, the temperature sensor can be used to temporarily increase the flow of water through the photocatalytic panel so that the ambient temperature water can carry heat out of the panel.

In a further aspect, the output product may be thermally driven from the photocatalytic panel to the storage tank. For example, it is known that methanol tends to readily evaporate in warm spaces and condense in cooler locations. Thus, in order to facilitate the flow of methanol from the building panel to the storage tank, the photocatalytic panel10is maintained at an elevated temperature. A thermal isolation layer185may be provided between the panel and the roof surface R to reduce heat transfer to the building. The photocatalytic panel may be warmed naturally from the solar energy and capable of maintaining a temperature above the boiling point of methanol (about 65° C.). At the same time, the storage tank182is maintained at a much lower temperature to induce heat convection from the photocatalytic panel to the tank.

In order to maintain the storage tank at a lower temperature regardless of ambient outdoor conditions, the tank182may be buried underground. Underground storage can maintain a generally uniform temperature of about 12° C. so that the resulting 50° C. temperature difference between building panel and storage tank will ensure a consistent flow of output product to the tank. Temperature and pressure sensors associated with the storage tank182can be used to trigger certain actions, such as bleeding off pressure within the tank, applying cooling, or even controlling the building panel to slow or stop the generation of output product.

The storage tank182may be associated with a single photocatalytic panel or a plurality of panels. The number of building panels served by a given storage tank can be determined by the output rate of the photocatalytic panels, the storage capacity of the tank, and the ability to sustain the thermal driving of the output products to the storage tank. Moreover, the storage tank(s) may be part of a larger system in which the contents of the tank(s) are pumped to a larger storage, processing or distribution system, much like a natural gas extraction system.

The photocatalytic panels and systems disclosed herein are well suited for removing carbon dioxide (CO2) from the atmosphere. On a large scale, widespread use of these building panels can help reduce the problem of CO2as a greenhouse gas. The building panels can be particularly concentrated around regions known to generate CO2emissions, such as in urban settings where vehicle emissions are prevalent and untreated. Not only do the photocatalytic panels disclosed herein help reduce the CO2content in the local atmosphere, they also convert that CO2into output products that have other utility, such as methanol.

The photocatalytic elements used with the photocatalytic panels disclosed herein may be of various known configurations, and of various known configurations for photocatalytic reduction of CO2. For instance, suitable photocatalytic elements may incorporate one or more of the following materials: porous graphitic carbon nitrides or carbamates to split CO2into CO and O2; ruthenium-rhenium based catalysts with triethylamin as a reducing agent operable for light at wavelengths less than 500 nm; Ru(2,2′)-bipyridine-2 with water to reduce the CO2to CO and H2; ZrO2with UV radiation to form CO and H2; and TiO2with water to reduce the CO2to methane (CH4) and methanol (CH3OH). Most of these prior approaches are inefficient and only produce meaningful output products with high concentrations of CO2, often concentrations well above the normal atmospheric levels. In some instances, it may be necessary to provide some means to enhance exposure of the photocatalytic element(s) to CO2.

In another aspect of the present disclosure, a photocatalyst or photocatalytic composition is presented that incorporates three functions necessary for CO2reduction, namely: i) CO2enrichment and activation; ii) effective absorption of sunlight; and iii) using energy from the sunlight to reduce the acquired CO2. With respect to the first function, it can be appreciated that the chemical reaction occurring in the photocatalyst will yield a satisfying rate of production of output product only if a sufficient concentration of CO2is available. Certain chemical species are known to bind or capture CO2at or near ambient temperature. However, the binding of the CO2must not be too strong to prevent release of the CO2for use in the catalytic reaction. In accordance with one aspect, a photocatalytic element for use in the building panels disclosed herein includes a composition or constituent capable of binding, capturing or adsorbing CO2from the air. The composition may include an amine group provided in a liquid or solid state depending upon the desired environment for the CO2capture, and capable or reversibly binding CO2. In a solid state, the amine group may include the chemical group of polysiloxanes, or graphitic carbonitrides (C3N4) with a terminating amine group. Alternatively, the composition may include a carbonate capable of binding CO2via reversible reaction to the bicarbonate state.

The second function, namely absorbing sunlight, is accomplished by a composition or constituent adapted to absorb sunlight, or more specifically certain wavelengths of light suitable for fueling the catalytic or photosynthesis reaction. Thus, strongly light absorbing groups or dyes are utilized that are stable even under strong direct sunlight. Suitable dyes may include: natural dyes, such as anthocyanine, anthochinone and carotinoide dyes; and synthetic dyes, such as polymethin, azo, triphenylmethan, antrachinone, alizarine, porphine or phthalocyanine dyes.

The third function of using the light energy to reduce the CO2may be accomplished with compositions useful for efficient light absorption, such as catalytic metals supported on oxides, such as ZrO2, SiO2, Al2O3and TiO2. Other suitable compositions may include other catalytic metals, such as Pt, Pd, Ru, Re, Fe and Co. These “reaction centers” may be embodied as a nano-catalyst for improved efficiency.

In accordance with one feature of the disclosed embodiments, each of the three functions is accomplished through a combination of the three compositions or constituents. In the combination it is important that the constituent performing the reduction of CO2be in very close proximity to the constituent that traps the ambient CO2, and in very close proximity to the constituent that traps the light energy. Preferably, the constituents are combined in a nanometer scale so that the gap between constituents is no more than a few nanometers to ensure rapid and complete communication of CO2and energy. In addition, at least the composition absorbing sunlight and the composition for reducing the atmospheric gas (CO2) are combined to permit electron energy transport between the compositions. This energy transport thus permits the efficient transfer of the energy from the sunlight captured by the sunlight absorbing composition to the “reaction center” compositions that use this energy to reduce the atmospheric gas.

In one embodiment, the three constituents are monomers that are combined into a single polymer. Thus, the polymer is formed from a first constituent or monomer A suitable for enhanced CO2adsorption, a second constituent or monomer B adapted to perform the photocatalytic function, and a third constituent or monomer C in the form of an efficient light absorbing dye adapted to perform the photocatalytic function. The photocatalytic element thus includes a layer of a polymer formed by the constituent monomers ABC. In one particular embodiment, the polymer may have the structure ABCABCABC . . . . This structure may ensure that all three functional blocks are closely fixed together on the nanometer scale.

In one embodiment, the polymer is formed by combining the three monomers A, B and C in a known manner. Thus, the three monomers may be mixed and then polymerized in a suitable process, such as a step-growth polymerization process or a condensation reaction, to achieve proper ordering and spacing of the monomers relative to each other in a repeating monomer chain ABCABC . . . . In this embodiment, the compositions selected for each of the three monomers have at least two reactive end groups. Moreover, the polymer is a conjugated system to enable energy transfer at the molecular level from the light absorbing monomer C to the photocatalytic monomer B. The resulting polymer may then be applied to a substrate and cured. Alternatively, the resulting polymer may have sufficient structural integrity when cured so that a supporting substrate is not required. The polymer produced by this process will limit the spacing between monomers to the nanometer range, such as spacings of 0.3-10.0 nm.

The constituent or monomer B is adapted to bond a component of the atmospheric gas. Thus, in the constituent B may be adapted to bind carbon from atmospheric CO2in the presence of water to produce an alcohol output product, and in some cases O2as an additional output product. In one specific example, a polymer is formed from an amine group for monomer A, a Phthalocyanine dye for monomer C and a siloxane based photocatalyst for monomer B. A chemical structure for the resulting polymer is shown inFIG. 10. The reaction of the polymer to exposure to CO2and sunlight in the presence of water yields CH3OH (methanol) and O2as output products, as depicted inFIG. 11. Since the monomer spacing is on the nanometer scale, the photocatalyst monomer B is close to monomer A for access to the adsorbed CO2and to monomer C for efficient energy transfer from the absorbed sunlight. The conjugated system within the polymer further facilitates the transfer of energy from monomer C to monomer B.

The composition formed by the three constituents A, B, and C may be modified to adjust the absorption of water used as a reaction partner. Thus, a fourth composition or constituent D may be added that includes a hydrophilic group or a hydrophobic group as needed to obtain a well-defined affinity for water. For instance, when the base polymer of monomer B (the photocatalyst monomer) is generally hydrophobic, the fourth constituent D may be a monomer selected from a hydrophilic group to ensure that a sufficient amount of water is present at the polymer for an effective reaction. Suitable hydrophilic groups may include aliphatic groups. Likewise, when the base polymer is generally hydrophilic monomer D is selected from a hydrophobic group to avoid deactivation of the amine group (monomer A) by protonation due to excess water. Suitable hydrophobic groups may include methyl groups.

In a further embodiment, the photocatalyst element may incorporate a liquid-based catalyst. In this embodiment, each of the constituents or monomers is dissolved in a solution, such as an aqueous solution. In some cases, a monomer may require connection to a hydrophilic group in order to ensure solubility in the aqueous solution. For instance, a light enhancing monomer A, such as a Phthalocyanine dye, may require connection to a hydrophilic group, such as an aliphatic group. Similarly, the nano photocatalyst may require coupling to a hydrophilic group for solubility. In one aspect, the pH of the solution may be maintained in the alkaline region by adding a suitable buffer that is not reactive with the functional groups in the solution.

It is contemplated that CO2will be enriched in the solution as carbonate or bicarbonate ions. The monomers are provided in sufficiently high concentrations to ensure close spacing between the three functional monomers, preferably in the nanometer range.

In certain embodiments, a voltage may be applied to the photocatalytic element to overcome reaction barriers and boost the desired reaction and output product generation. In these embodiments, the photocatalytic monomer B may be adapted to operate as an electrode in an aqueous solution having a suitable electrical conductivity. A second chemical electrode is incorporated in the aqueous solution. The photocatalytic monomer is preferably connected to the negative pole of the voltage generator to facilitate the reduction of the CO2. In this embodiment, a conductive photocatalyst element is desired, although a non-conductive photocatalyst element may be utilized if it is augmented with conductive materials, such as CNTs, graphenes, carbon black and the like.

It will be appreciated that the above described embodiments are merely exemplary, and that those of ordinary skill in the art may readily devise their own implementations and embodiments that incorporate the principles of the present invention and fall within the spirit and scope thereof. For instance, the photocatalytic elements of the embodiments disclosed herein are adapted to reduce CO2to useful output product(s). However, the photocatalytic elements may be adapted to reduce other atmospheric gases, such as deleterious greenhouse gases.