United States Patent: 8613900             

We begin to introduce herein, or reintroduce with an attempt to use proper terminology, a technical concept, or pathway, for the solar-powered conversion of Carbon Dioxide, as we could recover from the flue gases of our economically essential Coal-fired electric power generation plants, or, even from the atmosphere itself, into liquid and gaseous hydrocarbon fuels and chemicals.

In broad terms, the technology might be thought of as "artificial photosynthesis", as we've touched on in a few previous reports, such as, for two examples:

ARCO CO2 to Methanol Photosynthesis | Research & Development | News; concerning: "United States Patent 4,427,508 - Light Driven Photocatalytic Process; 1984; Assignee: Atlantic Richfield Company, CA;

Claims:  A method for the light driven photocatalytic reduction of carbon dioxide or the bicarbonate ion to at least one compound which comprises contacting silicon with a hydrogen containing material and at least one of carbon dioxide and the bicarbonate ion in the absence of separate physical electrolyte and electrodes, and conducting said contacting in the presence of light so that the energy of reduction is essentially supplied by said light. (And) wherein said light is one of artificial light, sunlight, or a combination thereof (and) wherein said compounds are carbon monoxide, alcohols, aldehydes, hydrocarbons, esters, and carboxylic acids ... (which are specified to include) methanol, formaldehyde, formic acid, and methane. There is provided, according to this invention, a method for the light driven photocatalytic reduction of carbon dioxide or the bicarbonate ion to at least one organic compound which comprises contacting silicon (elemental silicon) with at least one of carbon dioxide and the bicarbonate ion in the presence of light so that the energy of reduction is essentially supplied by said light"; and:

California Efficient CO2 to Methanol Photoelectric Conversion | Research & Development | News; concerning: "United States Patent 4,521,499 - Photoelectrochemical Electrodes and Uses Thereof; 1985; Assignee: Union Oil Company of California, Los Angeles; Abstract: A photoelectrode, containing a highly conductive coating material having a band gap (as specified)on a substrate containing a semiconductor material, is utilized in photovoltaic cells, photoelectrosynthesis and photoelectrocatalysis. ... The invention relates to photoelectrochemical electrodes and, more particularly, to the utilization of photoelectrochemical electrodes for producing electricity from semiconductor liquid junction photovoltaic cells and for producing stored energy products from photoelectrosynthetic and photoelectrocatalytic cells. ... Photoelectrosynthetic cells employing the photoelectrode of the invention may convert essentially any organic reactant in the presence of water to an oxidized organic product and hydrogen. Other examples of typical photoelectrosynthetic conversion reactions employing the photoelectrode of the invention include hydrogen chloride converted to hydrogen and chlorine, hydrogen bromide converted to hydrogen and bromine, hydrogen iodide converted to hydrogen and iodine, water and propylene converted to propylene oxide and hydrogen, and water and carbon dioxide converted to methanol and oxygen".

There are two chemical components to such light-driven, and other related, Carbon Dioxide utilization processes:

One is the chemical "reduction" of Carbon Dioxide, to form a more reactive compound, typically identified as Carbon Monoxide, although the chemistry can be more complex than that and different terms can be used to describe a chemically "activated", so to speak, Carbon Dioxide molecule, or fragment thereof.

The second is called, chemically, the "oxidation" of Water, H2O, in order to form, specifically, in addition to byproduct Oxygen, and instead of molecular Hydrogen, the Hydrogen "cation", abbreviated as "H+". See:

Hydrogen ion - Wikipedia, the free encyclopedia; "When hydrogen loses its electron ... cations can be formed (such as) 'H+'".

Such Hydrogen ions, cations, are so reactive that they can then serve to effect the nearly automatic, and concurrent, chemical reduction of Carbon Dioxide, with final reaction products including carbon monoxide, hydrocarbons, alcohols, and other chemicals.

Thus, the potential exists to design photosynthetic systems that -  - arising from perhaps less-sophisticated earlier developments like those disclosed in the above-referenced "US Patent 4,427,508 - Light Driven Photocatalytic Process" and "US Patent 4,521,499 - Photoelectrochemical Electrodes and Uses Thereof" - - much more efficiently, through an initial light-driven "water oxidation", with immediately subsequent or concurrent CO2 "reduction", convert blends of Carbon Dioxide and Water into Hydrogen-Carbon compounds, such as various hydrocarbons and alcohols.

That explanation is overly simplistic, and it's inadequacy reflects our own lack of education and sophistication in such matters, and our other personal insufficiencies. Certainly, there are qualified folks around in our Coal Country colleges and universities, and in some of our Coal Country chemical corporations, who could much more cogently and completely describe the concepts involved, if anyone happens to be genuinely interested enough to seek them out. Thankfully, there are also folks in the employ of our United States Department of Energy who do understand the meaning, and value, of such Solar-driven "Water Oxidation", for the generation of reactive Hydrogen ions, and the consequent, "CO2 Reduction", using the Hydrogen ions, to form hydrocarbons.

And, as seen in our reports of: 

USDOE 2013 Solar CO2 + H2O = Methanol + Methane | Research & Development | News; concerning: "United States Patent Application 20130256147 - Solar Fuels Generator; 2013; Inventors: Nathan S. Lewis and Joshua Spurgeon, CA; (Presumed eventual Assignee of rights: the California Institute of Technology); Abstract: The solar fuels generator includes an ionically conductive separator between a gaseous first phase and a second phase. A photoanode uses one or more components of the first phase to generate cations during operation of the solar fuels generator. A cation conduit is positioned provides a pathway along which the cations travel from the photoanode to the separator. The separator conducts the cations. A second solid cation conduit conducts the cations from the separator to a photocathode. Government Interests: This invention was made with government support under DE-SC000493/T-105066 awarded by the Department of Energy. The government has certain rights in the invention. ... The generator ... wherein the photoanode includes an oxidation catalyst (and) wherein the pathway extends from the oxidation catalyst to the separator (and) wherein: the photoanode extends outward from a first side of a separator; and a photocathode extends outward from a second side of the separator, the second side being opposite from the first side (and) wherein the cation conduit is in direct physical contact with the separator. The generator ...  wherein the first phase is a gas that includes water vapor, the second phase is a gas, and the photoanode is configured to use the water vapor to generate the cations. ... Another method of generating solar fuels includes using cations to generate the solar fuel (with) a photocathode in a gaseous second phase (and, a) separator being between the first phase and the second phase. The supply stream and/or the second phase can also include or consist of a reactant (in addition to water). (And, in some embodiments) CO2 serves as the reactant that is delivered to the photocathodes. Examples of the fuels that can be produced using this reaction in combination with the disclosed solar fuels generator include ... methanol, methane, ethanol"; and:

USDOE and California Solar Hydrogen for CO2-to-Fuel Conversion | Research & Development | News; concerning: "United States Patent Application 20130092549 - Proton Exchange Membrane Electrolysis Using Water Vapor as a Feedstock; 2013; Inventors: Joshua Spurgeon, Nathan Lewis and Philip Marcus;  Assignee: California Institute of Technology, Pasadena; Abstract: A light-driven electrolytic cell that uses water vapor as the feedstock and that has no wires or connections whatsoever to an external electrical power source of any kind. In one embodiment, the electrolytic cell uses a proton exchange membrane (PEM) with an IrRuOx water oxidation catalyst and a Pt black water reduction catalyst to consume water vapor and generate molecular oxygen and a chemical fuel, molecular hydrogen. The operation of the electrolytic cell using water vapor supplied by a humidified carrier gas has been demonstrated under varying conditions of the gas flow rate, the relative humidity, and the presence or absence of oxygen. The performance of the system with water vapor was also compared to the performance when the device was immersed in liquid water. Government Interests: This invention was made with government support under DE-SC0004993/T-105066 awarded by the Department of Energy. The government has certain rights in the invention. Claims: An illumination-driven apparatus, comprising: a separator having a first side and a second side opposite said first side, said separator configured to be permeable to an ionic reaction moiety and configured to be substantially impermeable to molecular moieties so as to separate a first molecular moiety present on said first side from a second molecular moiety present on said second side; an oxidation catalyst present on said first side of said separator, said oxidation catalyst configured to oxidize H2O to produce molecular oxygen; a reduction catalyst present on said second side of said separator, said reduction catalyst configured to reduce a substance to produce a chemical fuel (and) wherein said chemical fuel is a carbonaceous fuel (and, the) illumination-driven apparatus ... wherein said light absorber configured to absorb illumination is configured to absorb ... terrestrial solar illumination. A method of generating a chemical fuel and molecular oxygen from a reaction medium containing water vapor, comprising the steps of: providing an illumination-driven apparatus (with an) oxidation catalyst configured to oxidize H2O to produce molecular oxygen; a reduction catalyst present on said second side of said separator, said reduction catalyst configured to reduce a substance to produce a chemical fuel (and) wherein said reduction catalyst is a catalyst that reduces CO2 to produce a carbonaceous fuel. The method of generating a chemical fuel and molecular oxygen from a reaction medium containing water vapor (and) a reagent containing CO2 ... . In the issue of Chemical Reviews published on Nov. 10, 2010, Arthur J. Nozik and John Miller wrote in an editorial that "[t]he direct conversion of solar photons to fuels produces high-energy chemical products that are labeled as solar fuels; these can be produced through nonbiological approaches, generally called artificial photosynthesis. The feedstocks for artificial photosynthesis are H2O and CO2, either reacting as coupled oxidation-reduction reactions, as in biological photosynthesis, or by first splitting H2O into H2 and O2 and then reacting the solar H2 with CO2 (or CO produced from CO2) in a second step to produce fuels through various well-known chemical routes involving syngas, water gas shift, and alcohol synthesis";

our United States Department of Energy has begun to fund the development of light-driven, combined Water Oxidation and Carbon Dioxide Reduction technologies, wherein a process of "artificial photosynthesis" powered by "terrestrial solar illumination" can generate "solar fuels", like "methanol, methane (and) ethanol" from inputs of Water and Carbon Dioxide.

More information is becoming, and waiting to become, available about the USDOE's Artificial Photosynthesis, Carbon Dioxide and Water-to-fuels, program. For example, full reports of the USDOE contract work performed under the above-cited "DE-SC0004993/T-105066" have not yet been published; and, other, related contracts have been let by the USDOE, about which reports are also still pending. And, there is yet more background information we will be documenting for you in future reports. 

But, another report we made previously about the USDOE's focused development of Artificial Photosynthesis, Carbon Dioxide-to-Fuel technology is accessible via:

CoalTL: USDOE Hires California to Convert CO2 into Hydrocarbon Fuels | Research & Development | News; and concerns: "United States Patent Application 20120328505 - Nanostructured Transition Metal Oxides Useful for Water Oxidation Catalysis; 2012; Inventors: Heinz Frei and Feng Jiao, California and Delaware; Assignee: The Regents of the University of California; Abstract: The present invention provides for a composition comprising a nanostructured transition metal oxide capable of oxidizing two H2O molecules to obtain four protons. In some embodiments of the invention, the composition further comprises a porous matrix wherein the nanocluster of the transition metal oxide is embedded on and/or in the porous matrix. ... Government Interests: The invention was made with government support under Contract No. DE-AC02-05CH11231 awarded by the U.S. Department of Energy. The government has certain rights in the invention".

And, we learn herein that the above "United States Patent Application 20120328505", another end product document of another of those USDOE contracts related to the development of Artificial Photosynthesis technologies combining Solar-driven Water Oxidation and Carbon Dioxide Reduction, resulted in the recent, something of a Christmas Eve present, United States Patent we submit to you in this dispatch; wherein it's seen that, with USDOE sponsorship, improved catalysts have been developed - - catalysts which would seem suitable for use in the processes and devices disclosed in the above "US Patent Application 20130092549 - Proton Exchange Membrane Electrolysis Using Water Vapor as a Feedstock" and "US Patent Application 20130256147 - Solar Fuels Generator".

However, further study has revealed for us some ambiguity in the products/types of products generated by this Carbon Dioxide recycling and utilization catalytic technology, although, as revealed in the "Detailed Description" segment of the full Disclosure:

"The present invention has application in the energy industry. Catalytic water oxidation with visible light is a mandatory step of any technology for making a liquid fuel from water and carbon dioxide".

As we discuss via comments inserted in and appended to excerpts from the initial link in this dispatch to:

"United States Patent 8,613,900 - Nanostructured Transition Metal Oxides Useful for Water Oxidation Catalysis

Patent US8613900 - Nanostructured transition metal oxides useful for water oxidation catalysis - Google Patents

Nanostructured transition metal oxides useful for water oxidation catalysis - The Regents of the University of California

December 24, 2013

Inventors: Heinz Frei and Feng Jiao, CA and DE

Assignee: The Regents of the University of California

Abstract: The present invention provides for a composition comprising a nanostructured transition metal oxide capable of oxidizing two H2O molecules to obtain four protons. In some embodiments of the invention, the composition further comprises a porous matrix wherein the nanocluster of the transition metal oxide is embedded on and/or in the porous matrix.

Government Interests: The invention was made with government support under Contract No. DE-AC02-05CH11231 awarded by the U.S. Department of Energy. The government has certain rights in the invention.

Claims: A composition comprising a nanocluster consisting of a nanostructured transition metal oxide consisting of at least one of cobalt, iron, manganese, niobium, tungsten, or a mixture of two or more of said metals wherein said transition metal oxide is capable of oxidizing two H20 molecules to obtain four protons, and a porous matrix wherein the nanostructured transition metal oxide is embedded on and/or in the porous matrix. 

The composition ...  wherein the nanostructure is a nanorod and the nanocluster comprises a bundle of parallel nanorods (and) wherein two or more nanorods of the bundle of parallel nanorods are interconnected to each other by one or more short bridges (and) wherein each nanorod (is of sizes specified, and) wherein the nanocluster has a crystalline nature. 

The composition ...  wherein the transition metal oxide is Co3O4, MnO2, Mn2O3, or Mn3O4.

(Cobalt(II,III) oxide - Wikipedia, the free encyclopedia

Manganese dioxide - Wikipedia, the free encyclopedia

Manganese(III) oxide - Wikipedia, the free encyclopedia

Manganese(II,III) oxide - Wikipedia, the free encyclopedia - - all are known, understood, and available.) 

The composition ... wherein the porous matrix is a ... mesoporous silica scaffold.

(In plainer terms,  the Cobalt and/or Manganese Oxides are deposited in and on a sort of near-microscopic silca  "honeycomb".)

The composition ... wherein the porous matrix comprises a KIT-6 nanopore or SBA-15.

(We included a reference link in our earlier report of  "US Patent Application 20120328505" demonstrating that the above are known, established and available products. For more about them and the technology they embody than you really want to know, see:

http://www.icmr.ucsb.edu/programs/documents/Ryoo1.pdf; "'Nanoporous Materials: ordered mesoporous silica, non-oxides, and materials with pore hiearchy'; Preparative Strategies in Solid State and Materials Chemistry; 2010; Ryong Ryoo; Department of Chemistry, and Graduate School of Nanoscience and Technology; WCU; Korea".)

The composition (as specified, which) composition catalyzes the reaction:

CO2 + H2O = CH3OHO2 (under) visible light ..

(A note we inserted at this point in our prior report of 'US  Patent Application 20120328505 - Nanostructured Transition Metal Oxides Useful for Water Oxidation Catalysis" is this:

- - - "Above is one of the equations which we think needs fine-tuned. For clarity, we believe it should read:

'CO2 + H2O = CH3OH + O2 (under) visible light'.

And, as we take it, the Hydrogen freed from the Water by photo-catalysis is, again by photo-catalysis, being compelled to react with Carbon Dioxide, perhaps as held in solution with the Water, with the products being Methanol, "CH3OH", and Oxygen". - - -

However, further study - - again now absent the help of some knowledgeable folk who used to advise us before becoming totally frustrated by the apparent total lack of interest in all of this and abandoning the cause - - suggests to us - although keep in mind always our limitations - that such original assumption, while still feasible, could well be incorrect. Summed another way, the "CH3OHO2" could be written as "CH4O3", which is known as "Methane Triol" or "Orthoformic Acid"; which can be easily made to decompose into Formic Acid and Water. We've treated Formic Acid as one product of Carbon Dioxide hydrogenation previously in these reports; and, although a product of some commercial value and industrial utility now, it isn't the kind of stuff that would make you turn cartwheels. However, Formic Acid can be treated in various ways so that it can serve, separately, as a donator of both Hydrogen and Carbon Monoxide, which are reactive and which are useful in hydrocarbon synthesis technologies. Formic Acid could actually been seen and treated as a "carrier' of hydrocarbon synthesis gas, since the Hydrogen and the Carbon Monoxide that can be easily, again though separately, extracted from Formic Acid can be combined and treated together as hydrocarbon syngas; and, be catalytically, chemically condensed, as via for one example the Fischer-Tropsch process, and made to synthesize both gaseous and liquid hydrocarbons.)

Background and Field: The present invention is in the field of catalytic water oxidation. 

Currently the scientific community is investigating the specific problem of efficient catalytic water oxidation, which is a mandatory step of any sunlight to fuel conversion system, by exploring molecular organometallic catalysts or by using electrocatalytic metal oxide deposits in electrochemical cell configurations.

The present invention provides for a composition comprising a nanostructured transition metal oxide (which) is capable of oxidizing two H2O molecules to obtain four protons.

(The above "protons" would be the chemically reactive "H+" Hydrogen ions discussed in our introductory comments. They are reactive enough that they can combine with, and make new compounds from, the relatively inert Carbon Dioxide molecule.)

In some embodiments of the invention, the transition metal of the transition metal oxide is ... cobalt, iron, or manganese. In some embodiments, the Period 5 transition metal is nobelium. In some embodiments, the Period 6 transition metal is tungsten. In some embodiments, the transition metal oxide is Co3O4, MnO2, Mn2O3, or Mn3O4. In some embodiments, within one nanorod or nanocluster, the transition metal oxide can comprise either only one transition metal element, or a mixture of two or more transition metal elements. 

In some embodiments of the invention, the composition further comprises a porous matrix wherein the nanocluster of the transition metal oxide is embedded on and/or in the porous matrix. In some embodiments, the porous matrix is a mesoporous scaffold, such as a mesoporous silica scaffold.

The present invention also provides for a method of producing molecular oxygen from water comprising: (a) providing a composition comprising a nanostructured transition metal oxide of the present invention, and (b) contacting the water with the nanostructured transition metal oxide such that the nanostructured transition metal oxide catalyzes the water to produce molecular oxygen. 

The present invention also provides for a device comprising the composition comprising a nanocluster of a transition metal oxide.

The device can be a solar fuel device ... . 

Detailed Description: The present invention has application in the energy industry. Catalytic water oxidation with visible light is a mandatory step of any technology for making a liquid fuel from water and carbon dioxide ... .

The transition metal oxide nanocluster catalysts of the present invention can be incorporated in a variety of configurations and systems for sunlight to fuel conversion."

----------------------------

The full Disclosure of our subject, "United States Patent 8,613,900 - Nanostructured Transition Metal Oxides Useful for Water Oxidation Catalysis", is devoted for the most part to detailed description of how the "Metal Oxides", and what "Metal Oxides', can be transformed into "Water Oxidation" catalysts; and, thus, be formed into a "solar fuel device",  which, when exposed to sunlight, will, in essence, extract Hydrogen from Water, H2O, and, make that Hydrogen available for further, catalyzed reactions with Carbon Dioxide, with the end result  being, at least one embodiment of the catalytic composition, perhaps as used in the device disclosed, as in our above-cited report concerning it, by "United States Patent Application 20130256147 - Solar Fuels Generator; California Institute of Technology", "a liquid fuel made from water and carbon dioxide".

And, again, the making of that "liquid fuel from water and carbon dioxide" would be powered, in a process of "artificial photosynthesis", by freely available "sunlight".

There are, as noted, limits to our understanding here of the process and technology, as we're certain there will be for most who might stumble across this dispatch in the West Virginia Coal Association's R&D archives.

But, clearly:

Our United States Government confirmed, officially, through their allowance and publication of  "United States Patent 8,613,900", that, it is, again, feasible, using "sunlight' to drive the process, to make "liquid fuel ... from water and carbon dioxide".

And, it is  - -  without doubt,  question or justifiable objection - - way past time that the citizens of the United States of America, and especially those citizens resident in United States Coal Country, were not only fully and clearly informed of that fact, but, empowered to utilize it.


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