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      High-flux solar-driven thermochemical dissociation of CO2 and H2O using nonstoichiometric ceria.

      Science (New York, N.Y.)

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          Abstract

          Because solar energy is available in large excess relative to current rates of energy consumption, effective conversion of this renewable yet intermittent resource into a transportable and dispatchable chemical fuel may ensure the goal of a sustainable energy future. However, low conversion efficiencies, particularly with CO(2) reduction, as well as utilization of precious materials have limited the practical generation of solar fuels. By using a solar cavity-receiver reactor, we combined the oxygen uptake and release capacity of cerium oxide and facile catalysis at elevated temperatures to thermochemically dissociate CO(2) and H(2)O, yielding CO and H(2), respectively. Stable and rapid generation of fuel was demonstrated over 500 cycles. Solar-to-fuel efficiencies of 0.7 to 0.8% were achieved and shown to be largely limited by the system scale and design rather than by chemistry.

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          Most cited references6

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          Toward solar fuels: photocatalytic conversion of carbon dioxide to hydrocarbons.

          The past several decades have seen a significant rise in atmospheric carbon dioxide levels resulting from the combustion of hydrocarbon fuels. A solar energy based technology to recycle carbon dioxide into readily transportable hydrocarbon fuel (i.e., a solar fuel) would help reduce atmospheric CO2 levels and partly fulfill energy demands within the present hydrocarbon based fuel infrastructure. We review the present status of carbon dioxide conversion techniques, with particular attention to a recently developed photocatalytic process to convert carbon dioxide and water vapor into hydrocarbon fuels using sunlight.
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            High-rate solar photocatalytic conversion of CO2 and water vapor to hydrocarbon fuels.

            Efficient solar conversion of carbon dioxide and water vapor to methane and other hydrocarbons is achieved using nitrogen-doped titania nanotube arrays, with a wall thickness low enough to facilitate effective carrier transfer to the adsorbing species, surface-loaded with nanodimensional islands of cocatalysts platinum and/or copper. All experiments are conducted in outdoor sunlight at University Park, PA. Intermediate reaction products, hydrogen and carbon monoxide, are also detected with their relative concentrations underlying hydrocarbon production rates and dependent upon the nature of the cocatalysts on the nanotube array surface. Using outdoor global AM 1.5 sunlight, 100 mW/cm(2), a hydrocarbon production rate of 111 ppm cm(-2) h(-1), or approximately 160 microL/(g h), is obtained when the nanotube array samples are loaded with both Cu and Pt nanoparticles. This rate of CO(2) to hydrocarbon production obtained under outdoor sunlight is at least 20 times higher than previous published reports, which were conducted under laboratory conditions using UV illumination.
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              A monolithic photovoltaic-photoelectrochemical device for hydrogen production via water splitting

              Direct water electrolysis was achieved with a novel, integrated, monolithic photoelectrochemical-photovoltaic design. This photoelectrochemical cell, which is voltage biased with an integrated photovoltaic device, splits water directly upon illumination; light is the only energy input. The hydrogen production efficiency of this system, based on the short-circuit current and the lower heating value of hydrogen, is 12.4 percent.
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                Author and article information

                Journal
                21205663
                10.1126/science.1197834

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