http://phys.org/pdf334827714.pdf

We've noted for you that there exist some globally-organized groups focused on the development of artificial photosynthesis technology for the solar light-driven and productive chemical utilization of Carbon Dioxide.

Not well-publicized is the fact that our USDOE has been an active participant in those international groups, as can be learned via:

Solar Energy Innovation | Solar Fuels Instiute; "The SOFI team dreams big. We believe the development of a carbon neutral solar fuel is the greatest energy opportunity of our lifetime. Using just sunlight, carbon dioxide, and water, we can create a clean liquid fuel that could someday power our cars, airplanes, and homes without contributing to climate change"; and:

http://www.solar-fuels.org/members/our-members/;

wherein several of the USDOE's National Laboratories individually, in addition to the United States Joint Center for Artificial Photosynthesis, "JCAP":

Joint Center for Artificial Photosynthesis; "The Joint Center for Artificial Photosynthesis (JCAP) is the nation’s largest research program dedicated to the development of an artificial solar-fuel generation technology. Established in 2010 as a U.S. Department of Energy (DOE) Energy Innovation Hub, JCAP aims to find a cost-effective method to produce fuels using only sunlight, water, and carbon dioxide as inputs";

a consortium of USDOE laboratories and major US universities, are listed as active participants in the international "Solar Fuels Institute". 

One of the USDOE's labs listed as being active in that international Solar Fuels Institute is the Argonne National Laboratory in Chicago. And, as seen in our report of:

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; Inventor: Brian Ingram, et. al., IL and TN; Assignee: UChicago Argonne, LLC, Chicago (USDOE Argonne United States National Energy Technology Laboratory); 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. 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 (referred to herein as "solar-derived fuel" or "solar fuel"). In particular, the invention relates to wide band-gap photocatalytic materials, as well as the synthesis and surface modification thereof, as materials for promoting solar fuel production";

wherein sunlight powers the conversion of Carbon Dioxide, as recovered from whatever handy source, and "water vapor" into substitute natural gas Methane, they are assertively developing "Solar Fuel" technology for the productive utilization of CO2.

Another nation who's technical institutions are participating in the Solar Fuels Institute effort is Australia, where they do have plenty of sunshine to work with. An introduction to their efforts in the field is provided by the Australian Broadcasting Company:

http://www.abc.net.au/radionational/programs/futuretense/mimicking-nature-to-produce-the-energy-of-the-future/5747004;

"'Artificial photosynthesis: mimicking nature to produce the energy of the future'; 16 September 2014

Artificial photosynthesis - turning the energy of the sun into hydrogen and oxygen - could prove to be the ultimate in green, clean energy.

When a group of leading international scientists gathered in the UK recently they were dreaming of sunshine, but not in the way one might imagine.

Drawn from research institutions across the world, their mission was to plot the development of artificial photosynthesis, a technology that mimics the energy producing powers of plants and trees by taking sunlight, water and carbon dioxide and combining them to create fuel.

‘Essentially those plants are using sunlight as a source of energy to split water into hydrogen and oxygen,’ says the Australian National University’s Professor Thomas Faunce, the driving force behind the UK conference. 

‘That is what plants are doing across the earth at the moment, making hydrogen and oxygen: oxygen, which then goes off to create the atmosphere that allows us to breathe and keeps solar radiation away, and hydrogen, which can be used in a variety of different energy forms. So the simple vision we have is that we start doing our own photosynthesis.’

Despite being referenced by President Obama during his 2011 State of the Union speech, artificial photosynthesis remains virtually unknown outside of a relatively small circle of researchers. It’s rarely, if ever, discussed in relation to renewable energy.

Most developed nations now have artificial photosynthesis projects; the largest is America’s Joint Centre on Artificial Photosynthesis at Caltech—which was funded by the Obama administration with $122 million—but there is also a South Korean artificial photosynthesis project, a Chinese project, a Singaporean program at Nanyang University, and the Max Planck Institute in Germany, along with most European nations.

Australia has the Australian Research Council Centre of Excellence for Electromaterials Science". - - -

And, more about those Australian endeavors, which are actually the focus of our interest herein, can be learned via excerpts from the initial link in this dispatch to:

"'Artificial Photosynthesis: Creating fuel from sunlight' November 2014

Researchers have made significant progress towards developing a process of Artificial Photosynthesis (AP) that could replace the use of fossil fuels in the future. Artificial Photosynthesis is the industrial process of preparing fuels and chemicals from nothing more than carbon dioxide, water and sunlight.

In the latest issue of Advanced Energy Materials, researchers at Monash University have got a step closer to developing an AP process and have discovered a new way of converting carbon dioxide to methanol. Methanol is an extremely useful liquid fuel that could be used to run cars, heat homes or generate electricity in a fuel cell.

Professor Douglas MacFarlane, leader of the Energy Program at the ARC Centre of Excellence for Electromaterials Science (ACES) and ARC Laureate Fellow in the School of Chemistry at Monash University, said that research groups across the world had been tackling the challenge of AP; understanding the fundamental processes that take place in photosynthesis and mimicking them in an industrial process.

"If an artificial photosynthesis process can be developed that is significantly more efficient than plant-based photosynthesis, then it is conceivable that much of our fuel needs could be supplied from 'solar fuel' factories that would develop wherever sunshine and water are plentiful," said Professor MacFarlane.

"The key to this process in chemical terms is the development of new catalysts – one to oxidise water and another to absorb and reduce carbon dioxide. When the catalysts are coupled with materials that can absorb light energy, efficient generation of fuels such as methanol become possible."

Professor MacFarlane said the process had been achieved by the research team. "We have created a photo-catalyst based on copper oxide, the surface of which is decorated with tiny carbon dots of about 2 nano-metres in size. This nano-composite material can directly convert carbon dioxide dissolved in water to methanol using only sunlight as the energy source," he said.


"Methanol is directly useful as a fuel and can also be the building-block for many complex carbon
compounds such as plastics and pharmaceuticals."

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Key to Macfarlane's and Monash University's process for converting Carbon Dioxide into Methanol is actually the solar light-driven extraction of Hydrogen from water, H2O, since additional catalysts can then, as seen for one example in our report of:

Eastman Chemical Converts Carbon Dioxide into Fuel Alcohols | Research & Development | News; concerning: "United States Patent Application 20140243435 - Production of Methanol and Ethanol from CO or CO2; 2014; Inventors: Jan Hendrik Blank, et. al.; Assignee: Eastman Chemical Company, Kingsport, Tennessee; Abstract: This invention relates to a process for making methanol and ethanol from carbon dioxide and hydrogen. The process includes contacting a mixture of carbon dioxide and hydrogen with a catalyst system containing a ruthenium compound --and optionally, a chloride or bromide-containing compound--dispersed in a low-melting tetraorganophosphonium chloride or bromide salt under conditions effective to produce methanol and ethanol";

enable the direct catalyzed synthesis of fuel alcohols directly from Carbon Dioxide.

And, following, is disclosure of the Australian technology for extracting such valuable Hydrogen directly from the H2O molecule, in a process powered only by sunlight:

CATALYSTS AND METHODS OF USE - MONASH UNIVERSITY

"United State Patent Application 20140034510 - Catalysts and Methods of Use

United States Patent Application: 0140034510

Date: February 6, 2014

Inventors: Douglas Macfarlane, et. al, Australia

Assignee: Monash University, Australia

Abstract: The present invention relates to a catalyst comprising (i) a semiconductor preferably comprising one or more metal-(Group VIb) semiconductors, and (ii) a semiconductor material having elevated phosphorous content preferably comprising one or more metal-(Group VIb))-phosphorous species.

Claims:  A catalyst comprising: a semiconductor, and a semiconductor material having elevated phosphorous content (as defined and specified, and it's use) in a water splitting process.

Background and Field: The present invention relates to the field of catalysts. In one form, the invention relates to electrocatalysts, including photo-electrocatalysts. In a particularly preferred embodiment, the invention relates to the use of electrocatalysts for reduction processes, or oxidation processes such as water splitting.

The modern technological era relies on a steady, reliable supply of energy, for use in all aspects of everyday life. One of the most attractive ways to store and transport energy produced from renewable sources is based on splitting of water into oxygen and hydrogen. Water splitting is the separation of water into its constituents--oxygen (O2) and hydrogen (H2). Photo-electrochemical water splitting involves breaking down water into hydrogen and oxygen by electrolysis, but the electrical energy is supplied from a photo-electrochemical cell (PEC) process. This system is often colloquially referred to as `artificial photosynthesis`.

Photo-catalysis or photo-electrochemical splitting of water into hydrogen and oxygen can be used to collect and store energy on a global scale. In essence it consists of capturing energy and storing it in the form of chemical bonds to yield solar fuels which can be used as needed. Thus water splitting to produce hydrogen is a potentially major post-petroleum energy solution.

Catalysts according to the present invention would have many applications including the following: as electrodes or part of electrodes in conventional electrolysers for hydrogen production (and) in reduction processes, such as CO2 reduction".

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

By "reduction processes, such as CO2 reduction", they aren't speaking about a "reduction" in the amount of CO2 only, but, rather, the chemical process of "reduction", or, to put it another way, the "de-oxidation" of Carbon Dioxide, in order to make it a reactive species.

Again, as noted far above, and as seen again in:

USDOE Confirms CO2 to Methanol Economic Viability | Research & Development | News; concerning the USDOE's: "SANDIA REPORT SAND2009-7489; November 2009; Final Report on “Fundamentals of Synthetic Conversion of CO2 to Simple Hydrocarbon Fuels” Prepared by: Sandia National Laboratories, Albuquerque, New Mexico and Livermore, California; Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under Contract DE-AC04-94AL85000; Abstract: Energy production is inextricably linked to national security and poses the danger of altering the environment in potentially catastrophic ways. There is no greater problem than sustainable energy production. Our purpose was to attack this problem by examining processes, technology, and science needed for recycling CO2 back into transportation fuels. This approach can be thought of as “bio-inspired” as nature employs the same basic inputs, CO2/energy/water, to produce biomass. We addressed two key deficiencies apparent in current efforts. First, a detailed process analysis comparing the potential for chemical and conventional engineering methods to provide a route for the conversion of CO2 and water to fuel has been completed. No apparent “showstoppers” are apparent in the synthetic route. Opportunities to improve current processes have also been identified and examined. Second, we have also specifically addressed the fundamental science of the direct production of methanol from CO2 using H2 as a reductant. Energy production, or more precisely the conversion of resources to useful forms of energy, is the largest human enterprise on the planet. As such, it is inextricably linked to national security and quality of life, but also poses the danger of altering the environment in potentially catastrophic ways. Thus, there is no greater problem than sustainable energy production. ... As well, generating fuels from a noncrude oil source also aids in the economic stability and security of the United States. CO2 is an energy-depleted molecule - the conversion of a hydrocarbon to CO2 and H2O is a significantly downhill, exothermic process. In order to return this oxidized molecule (CO2) to a usable fuel, it must be converted (reduced) back into a suitable precursor. In order to do this, one can use ... an appropriate reducing agent such as H2. In the work discussed in this report, we assume that the reducing agent is H2, most likely eventually derived from photo-splitting of water. (We) specifically address the science of applying nanotechnology to the direct production of methanol from CO2, either chemically or electrochemically, using water, or H2 derived from water, as a reductant. Integrating CO2 capture and conversion into liquid fuels produces a new vision that promises the benefits of hydrogen while preserving many of the advantages of the hydrocarbon economy. In this section, we study the production of methanol from H2/CO2";

elemental, molecular Hydrogen enables the direct conversion of Carbon Dioxide into Methanol; and, as seen further in:

USDOE 2012 Coal Power Plant CO2 to Gasoline | Research & Development | News; concerning: "United States Patent 8,226,909 - Systems Including Catalysts in Porous Zeolite Materials Within a Reactor for Use In Synthesizing Hydrocarbons; 2012; Inventors: Harry Rollins, et. al., Idaho; Assignee: Battelle Energy Alliance, LLC, Idaho Falls; (USDOE Idaho National Laboratory); Abstract: Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. ... The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Government Interests: This invention was made with government support under Contract No. DE-AC07-05ID14517 awarded by the United States Department of Energy. The government has certain rights in the invention. Claims: A system for synthesizing hydrocarbon molecules having two or more carbon atoms from hydrogen and at least one of carbon monoxide and carbon dioxide ... . The present invention relates to catalytic materials, structures, systems, and methods ... for synthesizing hydrocarbon molecules from hydrogen and ... carbon dioxide using such catalytic structures. Carbon dioxide gas (CO2) may be converted into liquid fuels such as, for example, hydrocarbon molecules of between about 5 carbon atoms and about 12 carbon atoms per molecule (e.g., gasoline) through multi-step reactions";

a slightly more complex, "multi-step" process enables the direct production, through Methanol, of Gasoline from Carbon Dioxide and Hydrogen, as that Hydrogen might be photo-catalytically split from Water via the Monash University, of Australia, process of "United State Patent Application 20140034510 - Catalysts and Methods of Use".

And, even further, as seen for one example in:

NASA 2014 CO2 to Methane | Research & Development | News; concerning: "United States Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; 2014; Inventors: Christian Junaedi, et. al., CT; Assignee: Precision Combustion, Inc., CT; Abstract: A Sabatier process involving contacting carbon dioxide and hydrogen in a first reaction zone with a first catalyst bed at a temperature greater than a first designated temperature; feeding the effluent from the first reaction zone into a second reaction zone, and contacting the effluent with a second catalyst bed at a temperature equal to or less than a second designated temperature, so as to produce a product stream comprising water and methane. The first and second catalyst beds each individually comprise an ultra-short-channel-length metal substrate. An apparatus for controlling temperature in an exothermic reaction, such as the Sabatier reaction, is disclosed. Government Support: This invention was made with support from the U.S. government under U.S. Contract No. NNX10CF25P sponsored by the National Aeronautics and Space Administration. The U.S. Government holds certain rights in this invention";

Hydrogen also enables the conversion of Carbon Dioxide, in a chemical process that actually generates useable heat energy, into substitute natural gas Methane, a commodity that could prove of increasing value as the much ballyhooed shale gas fields fail - - as is proving out in the Barnett and Fayetteville shale fields in Texas and Arkansas - - to live up to their advance billing as pathways to inexpensive energy and United States independence in natural gas supply.

And, don't forget, that, as seen most recently in:

Renewable Energy Reclaims Coal Power Plant Carbon Dioxide | Research & Development | News; concerning: "United States Patent Application 20130152596 - Fossil Fuel-Fired Power Station Having a Removal Apparatus for Carbon Dioxide and Process for Separating Carbon Dioxide from an Offgas from a Fossil Fuel-Fired Power Station; 2013; Inventors: Hermann Kremer and Nicolas Vortmeyer, Germany; Assignee: Siemens Aktiengesellschaft (AG), Munich; Abstract: A fossil fuel-fired power station having a removal apparatus for carbon dioxide which is located downstream of a combustion facility and through which an offgas containing carbon dioxide may flow is provided. The removal apparatus comprises an absorption unit and a desorption unit. The desorption unit is connected to a renewable energy source";

just as we're getting better at using renewable energy to extract the needed Hydrogen from water, we're also getting better at using freely-available environmental energy to help make the extraction of the needed Carbon Dioxide from our Coal-fired power plant exhaust streams a less parasitic, more sensible proposition, as well.

In sum, valuable options are becoming available for us, wherein freely-available environmental energies enable the cost-effective extraction of Hydrogen from the abundant water, H2O, molecule, and, wherein that Hydrogen enables the efficient conversion of Carbon Dioxide, as we might conveniently and profitably recover from the stack gases of our Coal Country power plants, directly into a full range of liquid and gaseous hydrocarbon fuels.


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