United States Patent Application: 0140305805

Hey, wouldn't it be great if we could - - instead of harassing our economically essential Coal-fired generators of affordable and reliable electric power, or taxing their already over-taxed customers, because of essentially harmless Carbon Dioxide emissions - - harvest Carbon Dioxide, and then use and consume that CO2 in the efficient industrial synthesis of anything, basically, we now drive our entire nation into hock to keep buying from OPEC, or put our groundwater at risk to drill and frack for?

 

The United States Department of Energy says that we can.

If you've followed these reports at all, you'll know that virtually every single one of the USDOE's National Energy Technology Laboratories, even the USDOE National Renewable Energy Lab in Colorado, has said that we can convert Carbon Dioxide into hydrocarbon fuels and chemicals, and has demonstrated and disclosed the needed technologies for doing so. 

And, before proceeding, it seems timely to ask:

Since our United States Government can, as will be established herein again, efficiently convert Carbon Dioxide into any and all types of hydrocarbon fuels and chemicals, wouldn't the tax money we all pay to our United States Government now be far, far better spent reducing those CO2 utilization technologies to wide industrial practice - - thereby founding new industries, creating new jobs, and freeing our nation from economic bondage to OPEC - - than in continued harassment of our hugely productive Coal-fired power plants and all of the hard-working Coal-mining American companies and miners, and the families they support, that supply those power plants with Coal?

Have we all lost the simple guts it would take to stand up on our hind legs and start saying so?

Based on recent history and experience thus far, the tragic answer would now seem to be: Yes.

But, in case that sad conclusion is wrong, at least for some courageous few and independent-thinking individuals out there, herein is more evidence that our own Government knows full well that Carbon Dioxide is a valuable raw material resource.

First, though, we remind you of our report:

Chicago Converts CO2 into Methane and Ethylene | Research & Development | News; concerning: "United States Patent 4,897,167 - Electrochemical Reduction of CO2 to CH4 and C2H4; 1990; Assignee: Gas Research Institute, Chicago; Abstract: A process for electrochemical reduction of CO2 to CH4 and C2H4 providing both high current densities and high Faradaic efficiencies. The process is carried out in an electrochemical cell wherein copper is electrodeposited in situ on the cathode surface making freshly deposited copper available for the electrochemical reduction. Faradaic efficiencies of about 75 to about 98 percent for production of CH4 and C2H4 are obtained. Faradaic yields of hydrocarbons by the electrochemical reduction of CO2 according to this invention can be in order of 98 percent at 8.3 mA/cm2 and about 79 percent at an increased current density of 25 mA/cm2";

wherein, in Chicago, it was demonstrated that low-amperage, "8.3 (to) 25" milliamps per square centimeter, could convert up to "98 percent" of Carbon Dioxide, with water as the source of needed Hydrogen, into substitute natural gas Methane, CH4, and the simple hydrocarbon Ethylene, C2H4.

And, as seen in our report of:

USDOE Sunlight Converts CO2 into Methane | Research & Development | News; concerning: "US Patent Application 20130079577 - Synthesis of Photocatalysts for Solar Fuel Generation; 2013; Inventor: Brian Ingram, et. al., IL and TN; Assignee: UChicago Argonne, LLC, Chicago; (For six decades, the U.S. Department of Energy's (DOE's) Argonne National Laboratory has excelled in conducting scientific research in support of a secure future for the nation. From Argonne's inception, the University of Chicago has managed and operated the laboratory ... . Argonne is operated by UChicago Argonne, LLC). 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";

the USDOE's own Chicago-area Argonne National Laboratory has, as well, demonstrated the low-energy conversion of Carbon Dioxide into substitute natural gas Methane.

Herein, we see that the USDOE's Argonne Lab has gone on to further develop their Carbon Dioxide conversion processes, broadening the range of products, in addition to Methane, which can be made from CO2 and H2O, and further developing their catalytic systems so that low-voltage electricity, as perhaps could be generated from photovoltaic solar cells, can be used, to, as in the above-cited Gas Research Institute technology of "US Patent 4,897,167 - Electrochemical Reduction of CO2 to CH4 and C2H4", convert Carbon Dioxide and H2O into that broader array of hydrocarbon products. 

Comment follows and is inserted within excerpts from the initial link in this dispatch to:

"United States Patent Application 20140305805 - Subnanometer Catalytic Clusters for Water Splitting, Method for Water Splitting Using Subnanometer Catalyst Clusters

Patent US20140305805 - Subnanometer catalytic clusters for water splitting, method for splitting ... - Google Patents

SUBNANOMETER CATALYTIC CLUSTERS FOR WATER SPLITTING, METHOD FOR SPLITTING WATER USING SUBNANOMETER CATALYST CLUSTERS - UChicag

Date: October 16, 2014

Inventors: Stefan Vajda, et. al., Illinois

Assignee: UChicago Argonne, LLC, Chicago

(UChicago Argonne, LLC.; "Argonne National Laboratory, located just outside of Chicago and one of the U.S. Department of Energy's largest national laboratories for scientific and engineering research, is managed by UChicago Argonne, LLC, for the U.S. Department of Energy's Office of Science. The University of Chicago has served as prime contractor of Argonne since the lab’s founding in 1946 as an outgrowth of the Manhattan Project and the University's Metallurgical Laboratory".)

Abstract: The invention provides a catalytic electrode for converting molecules, the electrode comprising a predetermined number of single catalytic sites supported on a substrate. Also provided is a method for oxidizing water comprising contacting the water with size selected catalyst clusters. The invention also provides a method for reducing an oxidized moiety, the method comprising contacting the moiety with size selected catalyst clusters at a predetermined voltage potential.

(As will become clear, Carbon Dioxide, in addition to H2O, is the "oxidized moiety" being referred to.) 

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 catalytic electrode for converting molecules, the electrode comprising a predetermined number of single catalytic sites supported on a substrate (and) wherein the catalytic moiety is a metal selected from the group consisting of Palladium, Platinum, Cobalt, Iridium, Aluminum, Silver, Copper, Ruthenium, Iron, and combinations thereof.

The electrode ... wherein the substrate is an electrically conductive material selected from the group consisting of such as (ultra)nanocrystalline diamond, graphite, graphene, carbon nanotubes and other; (ii) oxides such as alumina, iron oxide, copper oxide, titania, magnesium oxide, zinc oxide, zirconium oxide, hafnium oxide, tungsten oxide (iii) metals such as copper, silver, aluminum, tantalum, tungsten and combinations thereof.

A method for oxidizing water comprising contacting the water with size selected catalyst clusters.

The method as recited in claim 10 wherein the pH of the method is greater than about 12 (and) wherein the method utilizes electrolysis and the voltages applied up to approximately 3V (and) wherein the method is practiced at a temperature ranging between approximately 5 and 900 C.

Background, Field and Summary: This invention relates to an electrode and a method for facilitating electrochemical reactions, and more specifically this invention relates to an electrode and a method for utilizing size selected catalyst clusters to facilitate oxidizing and reducing reactions.

(http://www.freepatentsonline.com/20140305805.pdf; - the link is to page 4 of the full United States Patent Application 20140305805 document file, but is designated as "Sheet 3 of 4". It clearly illustrates that the "oxidizing and reducing reactions" include the splitting of both Water and Carbon Dioxide, and the consequent generation of products that include Carbon Monoxide, Methane, Ethylene and Methanol.)

Efficient methods for splitting water are a key scientific challenge for meeting the world's fuels needs over the next century. Water oxidation (i.e., water splitting) is a key catalytic step for electrical fuels generation. It consists of two reactions: the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER).

A need exists in the art for a catalyst system and a method for catalysis that is applicable to many reactions, including water electrolysis. The system and method should either completely eliminate, or minimize the use of precious metals. The system and method should also be self-healing so as to extend the longevity of the system, and thereby enhance the efficiency and economics of catalysis processes. And the system and method should incorporate catalytic materials having reduced over potentials and increased turnover rates.

An object of the invention is to provide a water splitting system that overcomes many of the drawbacks of the prior art (and another) object of the present invention is to provide electrocatalysts for water decomposition. A feature of the invention is the use of clusters of catalysts, wherein each of the clusters contain no more than about 50 atoms of catalytic moiety, preferably between 3 and 50 atoms and more preferably between 4 and 30 atoms. An advantage of the invention is achieving the highest utilization of catalyst, thereby rendering the electrocatalysts very economical to use.

Yet another object of the present invention is providing a self-healing catalyst system. A feature of the invention is the use of some sized metal catalytic clusters (such as clusters consisting of 4-50 metal atoms of catalytic material) to eliminate support structure defects by covering them, (i.e. isolating them from direct exposure to the environment) and therefore passivating them. An advantage of the invention and the use of relatively higher atom containing clusters on the same passivated support to enable catalytic reactions. This enhances the activity of the catalyst while extending the useful lifetime of the entire electrode.

Briefly, the invention provides a catalytic electrode for converting molecules (and) a method for oxidizing water comprising contacting the water with size selected catalyst clusters.

The invention also provides a method for reducing an oxidized moiety, the method comprising contacting the moiety with size selected catalyst clusters at a predetermined voltage potential. In an embodiment of the invention, the voltages applied in the method range from between approximately -2 V and +2.5 V with respect to the standard hydrogen electrode. This voltage range enables electrolysis related to oxygen evolution, hydrogen evolution and CO2 reduction, and also high temperature electrolysis protocols as also described herein.

(The) system also is applicable in reduction scenarios, for example in the reduction of carbon dioxide via the schematic depicted in FIG. 3. In this scenario, water splitting is combined with CO2 conversion to produce fuels and or other valuable feedstocks."

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The above-noted "FIG. 3" is accessible via the link included above to page 4 of the full patent application document.

Again, the "fuels and ... valuable feedstocks" which can be produced, from Carbon Dioxide, with "voltages applied up to approximately 3V", which even relatively lame solar arrays should be able to gin up even on partly cloudy days, include such seemingly-valuable materials, among several specified, as substitute natural gas Methane, "CH4", and fuel alcohol Methanol, "CH3OH".

And, as we'll eventually get around to documenting and discussing in more detail in reports to follow, as seen for one example in our prior report of:.

Japan CO2 to Methanol to Gasoline | Research & Development | News; concerning, in part: "United States Patent Application 0130014430 - Method for Generating Electricity and for Producing Gasoline from Methanol and System Therefore; 2013; Inventor: Masaki Iijima, Japan; Assignee: Mitsubishi Heavy Industries, Ltd., Tokyo; A method for generating electric power and for producing gasoline from methanol, includes the steps of: synthesizing gasoline by reacting methanol under a catalyst; recovering heat generated from the gasoline synthetic reaction of methanol by cooling the reaction with coolant to vaporize the coolant; and generating electric power by using the coolant vapor produced in the heat recovery. The power generation step may include generating electric power with a plurality of steam turbines in series, e.g., a high-pressure turbine, a medium-pressure turbine, and a low-pressure turbine. Claims: A method for generating electric power and for producing gasoline from methanol";

Methanol, as made perhaps via the catalytic process disclosed by our subject herein, the USDOE Argonne National Laboratory's "US Patent Application 20140305805 - Subnanometer Catalytic Clusters for Water Splitting, Method for Water Splitting Using Subnanometer Catalyst Clusters", from nothing more than Carbon Dioxide and Water, can be converted directly and efficiently into non-OPEC, "renewable" Gasoline in a process that isn't just efficient but is, as well, exothermic, and allows for the generation of a certain amount of by-product electricity with the Gasoline.

And, yet again, our own United States Government has demonstrated that Carbon Dioxide is a valuable raw material resource, which we could, and should, create new industries and new jobs by harvesting and then converting into "fuels and or other valuable feedstocks".


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