United States Patent Application: 0120328505
We introduce to you herein a concept, and a terminology, that for a long time eluded us; and, to a large extent, still does.
If any of the half-dozen or so United States Coal Country journalists who are the primary addressees of these dispatches ever become motivated enough to simply ask their kid's high school chemistry teacher for an explanation, we're certain the matter could be easily exposed and described to you, the United States Coal Country public, in understandable terms.
That, inexplicably, seems now an unlikely eventuality, and, for sad reasons we won't belabor you with, that simple option is not available to us. So, we'll do our best to muddle through it all, and ask for your patience as we attempt to do so.
There exists a chemical process in general referred to as "water oxidation"; and, why it is so labeled, we have no idea. It is not the same sort of "oxidation" that, for instance, wood undergoes in your fireplace to produce light and heat; nor, is it the same as steel and iron undergo to produce rust.
When Water, H2O, is "oxidized", even though it is chemically already "Hydrogen Oxide", or even more specifically, Dihydrogen Monoxide, a dangerous-sounding substance that, indeed, as explained via:
Dihydrogen monoxide hoax - Wikipedia, the free encyclopedia;
is fatal if inhaled and contributes to the erosion of our natural landscape, it actually means that, in a way, the Hydrogen of which H2O is in part composed is getting freed up, and being made available for reaction with other elements. And, one of the elements with which it can be made to react is Carbon, as that Carbon might be found in Carbon Dioxide.
The end products of such water oxidation reactions - - when forced by applied energy, such as sunlight, to take place in the presence of Carbon Dioxide, and when properly catalyzed - - can be molecular Oxygen, O2, and, familiar sorts of hydrocarbon compounds, like the liquid fuel alcohol, Methanol.
The representative of light-driven water oxidation technology we bring to you herein doesn't explain it all as well as some others we will bring to you in the near future do. Those other expositions of related and closely similar water oxidation technology describe it, we think, a bit more understandably, and perhaps correctly; and, we will eventually get those to you.
We're starting with this one, though - - even though this is an early version of a patent application and some chemical formula presented seem incorrectly expressed to us and will, hopefully, be corrected or at least expanded as the application proceeds - - since your tax dollars paid for it, you will be the owners of it, and you deserve a full and complete explanation of what it's all about.
First, for a little background on what is being technically addressed herein, which is more fully, and more correctly, known as "heterogeneous" water oxidation, you might want to read through:
Heterogeneous water oxidation - Wikipedia, the free encyclopedia.
And, as you will see herein, the University of California, home of the USDOE's Lawrence Berkeley National Laboratory, was engaged by the United States Department of Energy to undertake the development, as they explain via:
Turning Sunlight into Liquid Fuels: Berkeley Lab Researchers Create a Nano-sized Photocatalyst for Artificial Photosynthesis «; from March 10, 2009, wherein it's stated, that: "A goal of scientists has been to develop an artificial version of photosynthesis that can be used to produce liquid fuels from carbon dioxide and water. Researchers with the U.S. Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) have now taken a critical step towards this goal with the discovery that nano-sized crystals of cobalt oxide can effectively carry out the critical photosynthetic reaction of splitting water molecules. ... (Chemists) with Berkeley Lab’s Physical Biosciences Division, have been investigating metal oxide catalysts for the production of liquid fuels through artificial photosynthesis. "Photooxidation of water molecules into oxygen, electrons and protons (hydrogen ions) is one of the two essential half reactions of an artifical photosynthesis system - it provides the electrons needed to reduce carbon dioxide to a fuel,” said Heinz Frei, a chemist with Berkeley Lab’s Physical Biosciences Division, who conducted this research with his postdoctoral fellow Feng Jiao. “Effective photooxidation requires a catalyst that is both efficient in its use of solar photons and fast enough to keep up with solar flux in order to avoid wasting those photons. Clusters of cobalt oxide nanocrystals are sufficiently efficient and fast, and are also robust (last a long time) and abundant. They perfectly fit the bill.” This research was performed through the Helios Solar Energy Research Center (Helios SERC), a scientific program at Berkeley Lab ... , which is aimed at developing fuels from sunlight. Frei serves as deputy director of Helios SERC";of a system of "artificial photosynthesis" that, using nothing but sunlight to power the process, converts, via a process of Water Oxidation, a mix of Water and Carbon Dioxide into liquid hydrocarbon fuel.
And, note: Though not well-chronicled, we believe and consider the above-named "Helios" project to be a direct evolution of the very similar USDOE "Green Freedom (TM)" project and technology about which we've previously reported, as in:
West Virginia Coal Association | USDOE "Green Freedom" CO2 Recycling | Research & Development; concerning: "Green Freedom (TM) - A Concept for Producing Carbon-Neutral Synthetic Fuels; 2007; Los Alamos National Laboratory, NM; We have developed a low-risk, transformational concept, called Green Freedom (TM), for large scale production of carbon-neutral, sulfur-free fuels and chemicals from air and water. Green Freedom (TM) utilizes carbon-neutral power to recover carbon dioxide from the atmosphere; split water into hydrogen; and, convert hydrogen and carbon dioxide into synthetic fuels and organic chemicals";
which itself was founded on earlier USDOE CO2-recycling innovations, like that disclosed, for one example, in our report of:
West Virginia Coal Association | USDOE Recycles CO2 to Methanol with Solar Power | Research & Development; concerning: "United States Patent 6,066,187 - Solar Reduction of CO2; 2000; Government Interests: This invention was made with government support ... (from) the U.S. Department of Energy to The Regents of the University of California. The government has certain rights in the invention. Abstract: The red shift of the absorption spectrum of CO2 with increasing temperature permits the use of sunlight to photolyze CO2 to CO. The process of the present invention includes: preheating CO2 to near 1800 K; exposing the preheated CO2 to sunlight, whereby CO, O2 and O are produced; and cooling the hot product mix by rapid admixture with room temperature CO2. The excess thermal energy may be used to produce electricity and to heat additional CO2 for subsequent process steps. The product CO may be used to generate H2 by the shift reaction or to synthesize methanol";
wherein Solar thermal energy powered the conversion of Carbon Dioxide into Carbon Monoxide, and thence into the liquid fuel alcohol, Methanol.
Comment follows and is inserted within excerpts from the initial link in this dispatch to:
"United States Patent Application 20120328505 - Nanostructured Transition Metal Oxides Useful for Water Oxidation Catalysis
Date: December 27, 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.
(The true import of this technology is revealed only in one statement of claims, as we will highlight.)
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 nanostructured transition metal oxide capable of oxidizing two H2O molecules to obtain four protons, and a porous matrix wherein the nanostrcutured 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.
(Don't be distracted by the descriptor "nano". As we've explained in previous reports, it just means really, but not impossibly, small; and, there are specific size ranges which qualify as "nano".)
The composition ... wherein the nanocluster has a crystalline nature (and) wherein the transition metal of the transition metal oxide is ... cobalt, iron, or manganese (and/or) nobelium (and/or) tungsten.
The composition ... wherein the transition metal oxide is Cobalt Oxide (or a Manganese Oxide, as specified).
The composition ... further comprising a second transition metal oxide (and) comprising a mixture of two or more transition metal elements.
The composition ... wherein the porous matrix is a mesoporous silica scaffold.
The composition ... wherein the porous matrix comprises a KIT-6 nanopore or SBA-15.
(Although those of us regular working, or one way or another retired, stiffs have never heard of them, the above are what are known as "molecular sieves"; and, in recent decades such molecular sieves have become better known and more widely used in chemical processing industries. See, for example:
Rapid synthesis of mesoporous SBA-15 molecular sieve by a microwave–hydrothermal process - Chemical Communications (RSC Publis ; "'Rapid Synthesis of Mesoporous SBA-15 Molecular Sieve'; November, 2000; The Pennsylvania State University and Saga Ceramics Research Laboratory, Japan".
The point being that "KIT-6 nanopore or SBA-15" aren't just "made-up" names and numbers. They're real stuff that is available, and well-known to certain chemical processing specialists.)
The composition ... wherein the composition catalyzes the reaction:
CO2 + H2O = CH3OH O2 visible light with a turnover frequency (TOF) (as specified).
(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.
And, we take the opportunity to remind you, that, not only can Methanol be used and consumed in the further synthesis of certain plastics, wherein the CO2 consumed, as herein, in the synthesis of the Methanol would be permanently, and productively, sequestered, but, as seen for one example in our report of:
West Virginia Coal Association | ExxonMobil "Coal to Clean Gasoline" | Research & Development; concerning: "'Coal to Clean Gasoline'; Xinjin Zhao, Ron D. McGihon and Samuel A. Tabak; ExxonMobil Research and Engineering Company, USA, discuss ExxonMobil's methanol to gasoline technology for the production of clean gasoline from coal. ExxonMobil’s methanol-to-gasoline (MTG) process efficiently converts crude methanol to high quality clean gasoline. When coupled with commercially proven coal gasification and methanol synthesis technology, MTG offers an effective route to premium transportation fuel from coal";
Methanol, no matter which of our precious and abundant natural resources, whether Carbon Dioxide or Coal, we make it from, can be further converted directly into Gasoline - something we now seem willing to fight foreign wars and mortgage our grandchildren's future to the inimical, alien nations of OPEC to keep ourselves supplied with in the here and now.)
The device (as claimed) is a solar fuel device or a photoelectric device.
A method of producing molecular oxygen from water (wherein) the nanostructured transition metal oxide catalyzes the water to produce molecular oxygen.
(We won't beat it to death with more reference links, but the byproduct "molecular oxygen" could be sold to help offset the costs of the CO2-to-Methanol production, or, simply used in a Coal gasification system to generate, via a totally separate process and procedure, as indicated in our above citation of ExxonMobil, more Methanol.)
Background and Field: The present invention is in the field of catalytic water oxidation.
Currently there is no artificial photosynthetic system that converts carbon dioxide and water with sunlight to a liquid fuel. Such a system needs to be sufficiently efficient for keeping up with the incident flux of solar photons, must be durable, made of Earth abundant materials and with scalable synthetic methods.
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 best available molecular catalysts using Earth abundant metals are still far too slow for keeping up with the solar flux, and are unstable. Metal oxide layers of abundant elements deposited onto various metal anodes, especially metal oxides of Co and Mn, are known to catalyze water oxidation typically under harsh (very basic) pH conditions.
Summary: The present invention provides for a composition comprising a nanostructured transition metal oxide. The nanostructured transition metal oxide can be in a nanocluster. The nanostructured transition metal oxide is capable of oxidizing two H2O molecules to obtain four protons.
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 or a photoelectric device.
In some embodiments of the invention, the composition catalyzes the reaction:
CO2 + H2O = CH3OH + O2."
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Our United States Government has developed the technology to convert Carbon Dioxide and Water into Methanol, using only sunlight to power the process, just as, as seen in:
West Virginia Coal Association | USDOE Sunlight Converts CO2 into Methane | Research & Development; concerning: "US Patent Application 20130079577 - Synthesis of Photocatalysts for Solar Fuel Generation; 2013; Assignee: UChicago Argonne, LLC, Chicago; Abstract: In one preferred embodiment, a photocatalyst for conversion of carbon dioxide and water to a hydrocarbon and oxygen ... . Government Interests: The United States Government has rights in this invention pursuant to Contract No. DE-AC02-06CH11357 between the United States Government and UChicago Argonne, LLC representing Argonne National Laboratory. Claims: A photocatalyst for conversion of carbon dioxide and water into a hydrocarbon and oxygen (and, a) method of converting carbon dioxide and water into a hydrocarbon ... . This invention relates to the energy efficient photocatalytic conversion of carbon dioxide gas and water vapor to methane and other hydrocarbon fuels, particularly promoted by sunlight";our United States Government has developed the technology to convert Carbon Dioxide and Water into Methane, using only sunlight to power the process.
Now, just thinking off the tops of our heads, it's our guess that a number of different types of people comprising the public in United States Coal Country, both Coal Miners, whose way of life and very livelihoods are threatened by predatory Cap and Trade CO2 taxation, and, committed environmentalists, who might genuinely be concerned, among other, perhaps pertinent, things, with the effects of CO2 in our atmosphere - - oh, and let's not forget anyone, at all, whose had to send a son or daughter off to fight in a Middle East or Arabian oil war - - just might be interested in the fact that freely-available sunlight, in processes owned by the United States Government, developed in programs paid for by United States income taxes levied against nearly every United States citizen, can convert Carbon Dioxide, as recovered from whatever handy source, into domestically-derived, environmentally-friendly liquid fuel for transportation and domestically-derived, environmentally-friendly substitute natural gas.
That's a pretty broad public constituency, which begs what we think to be a simple, valid question:
What interest is served by continued public silence concerning the fact?