France 1982 Solar CO2 to Syngas

http://www.pnas.org/content/79/2/701.full.pdf

Carbon Dioxide, as it is co-produced in only a small way, relative to some all-natural, un-taxable and apolitical sources of it's emission, such as the Earth's inexorable processes of planetary volcanism, by our economically essential use of Coal in the generation of reliable and affordable electric power, can be seen and treated as a valuable raw material resource.

As we've documented many times in recent years, more lately for just one example in our report of:

The USDOE Converts More Coal Exhaust CO2 into Gasoline | Research & Development | News; concerning: "United States Patent Application 20140272734 - Electrochemical Device for Syngas and Liquid Fuels Production; 2014; Inventors: Robert Braun, William Becker, and Michael Penev, CO; (USDOE National Renewable Energy Laboratory and Colorado School of Mines); Abstract: The invention relates to methods for creating high value liquid fuels such as gasoline, diesel, jet and alcohols using carbon dioxide and water as the starting raw materials and a system for using the same. These methods combine a novel solid oxide electrolytic cell (SOEC) for the efficient and clean conversion of carbon dioxide and water to hydrogen and carbon monoxide, uniquely integrated with a gas-to-liquid fuels producing method. Government Interests: This invention was made with government support under award number KXEA-3-33607-54 awarded by the National Renewable Energy Laboratories (NREL). The U.S. Government has certain rights in the invention";

the science and technology for harnessing so-called "renewable" energy of one form or another to drive chemical processes that break Carbon Dioxide, as harvested from whatever convenient source, and Water down into their simpler constituents, Carbon Monoxide, Hydrogen and Oxygen, have lately been seeing intensive development by various companies, universities and governments literally around the world.

As stated clearly by the USDOE/NREL and it's contractors in the above "United States Patent Application 20140272734 - Electrochemical Device for Syngas and Liquid Fuels Production", the Carbon Monoxide and Hydrogen products of such CO2 and H2O decomposition comprise a hydrocarbon synthesis gas which can, via long-known and established processes such as for example the Fischer-Tropsch synthesis, then be catalytically, chemically condensed into hydrocarbon fuels, "such as gasoline, diesel, jet and alcohols".

However, as we've also documented from time to time, that concept of converting Carbon Dioxide and Water into hydrocarbon synthesis gas has been known and to a certain extent worked with for many decades, including in other nations of the world.

And, as we learn herein, the additional concept of using one form or another of renewable energy to drive those processes of CO2 and H2O decomposition, to form syngas, has as well been around for a long time and, in other parts of the world, studied and developed.

Comment follows excerpts from the initial link in this dispatch to:

"Photochemical Generation of Carbon Monoxide and Hydrogen by Reduction of Carbon Dioxide and Water Under Visible Light Irradiation

http://www.pnas.org/content/79/2/701.full.pdf?sid=e9e91325-c16e-4820-b9cd-889a22b9d087

Proceedings of the National Academy of Science, USA; Volume 79, pages 701-704

January, 1982

Jean-Marie Lehn and Raymond Ziessel

Institut Le Bel, Universite Louis Pasteur; Strasbourg, France

Abstract: Visible light irradiation of solutions of Ruthenium(2,2'-bipyridine)2+, cobalt(ll) chloride, and carbon dioxide in acetonitrile/water/triethylamine generates simultaneously carbon monoxide and hydrogen.

The reaction involves photoinduced reduction of CO2 and H20, triethylamine serving as electron donor in
the Ru(2,2'-bipyridine)2+/Co2+ system.

The amount of gas (CO+ H2) produced and the selectivity ratio CO/H2 depend markedly on the composition of the system.

Addition of free bipyridine strongly decreases CO generation but increases H2 production. With different tertiary amines, both the quantity (CO + H2) and the ratio CO/H2 increase markedly ... .

Higher selectivity for CO2 reduction to CO in preference to water reduction occurs when triethanolamine
is used instead of triethylamine.

CoCl2 is the most efficient mediator for both CO and H2 generation and specifically promotes CO formation, whereas salts of other cations studied only yield H2.

These processes represent an abiotic photosynthetic system allowing simultaneous generation of CO and H2 and regulation of the CO/H2 ratio.

Mechanistic studies and explorations of other components that may increase efficiency and product selectivity should be carried out. The results obtained are also of significance for solar energy conversion with consumption of a pollutant, CO2.

Photoinduced splitting of the water molecule and reduction of carbon dioxide are the basic reactions of natural photosynthesis. They represent a fascinating area of chemical research, from both the fundamental point of view-understanding the mechanism of the natural processes and devising artificial photosynthetic
systems that perform these reactions in the laboratory-and the practical point of view-devising means for the photochemical conversion and
storage of solar energy by producing fuels (hydrogen, carbon monoxide, methanol, methane, for instance).

The results (of described experimental development work) lead to the (conclusion): The present system (as described) is capable of generating simultaneously CO and H2 by reduction of CO2 and H2O under irradiation with visible light.

The present work describes a photochemical process which produces simultaneously CO and H2 by reduction of CO2 and H2O.

It represents a further step in the development of chemical systems capable of artificial photosynthesis and solar energy conversion and storage.

Finally, one may note that the simultaneous reduction of CO2 and H2O produces in fact "synthesis gas" (CO + H2), which is of interest for large scale industrial processes".

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This work pertaining to "artificial photosynthesis" - - showing that solar light energy can be used to convert Carbon Dioxide and Water into hydrocarbon synthesis gas blends of Carbon Monoxide and Hydrogen, which can then be used to manufacture fuel alcohol "methanol", substitute natural gas "methane", etc., and, as per the USDOE's NREL in "United States Patent Application 20140272734 - Electrochemical Device for Syngas and Liquid Fuels Production", "high value liquid fuels such as gasoline, diesel, jet" - - might have been accomplished in France.

But, it was openly published more than three decades ago in the United States of America.

Given the many, uncountable sacrifices we, in the USA, as a nation have made to keep buying stuff like "gasoline" and "diesel" from OPEC in the many years since these facts were made public; and, given the many specious threats that have been raised against our economically essential Coal-fired power generation industries because of their emissions of Carbon Dioxide, it is inexplicable, inexcusable, that the facts represented herein, where simple sunlight can power the conversion of Carbon Dioxide, through formation of hydrocarbon synthesis gas, into "methanol", "methane", "gasoline" and "diesel", have not been openly and honestly reported to us all, especially all of us living and working in United States Coal Country.

That, especially, since, as seen for just one more recent example in our report of:

New York City Sunlight Converts CO2 into Synthetic Natural Gas | Research & Development | News; concerning: "United States Patent 8,992,738 - Method for Conversion of Carbon Dioxide to Methane Using Visible and Near Infra-Red Light; 2015; Inventor: Harry D. Gafney, NY; Assignee: Research Foundation of the City University of New York, NYC; Abstract: The invention relates to a method for converting carbon dioxide to methane";

such processes of "artificial photosynthesis", in which Carbon Dioxide is recycled into hydrocarbons, or hydrocarbon precursors in reactions powered by at least part of the solar spectrum, have become, even in the USA, more sophisticated, and even product-specific.

It is almost beyond comprehension that we, any of us aware of such developments, wouldn't, given the seeming value of such information, make at least some effort to openly educate about and promote such technology among our fellow citizens for all our benefit, and to the confounding of both our common United States of America international competitors and our outright enemies.

Where, in the world, have all our genuine United States patriots fled to?