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      Exploring the properties and applications of nanoceria: is there still plenty of room at the bottom?

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          Abstract

          Nanoceria is an exceptionally versatile, commercially valuable catalytic material whose properties vary dramatically from that of the bulk material.

          Nanoceria is an exceptionally versatile, commercially valuable catalytic material whose properties vary dramatically from that of the bulk material. Nanoceria's redox properties can be tuned by choice of method of preparation, particle size, nature and level of dopant, particle shape and surface chemistry. The two oxidation states of the cerium element in the lattice make possible the formation of oxygen vacancies which are essential to the high reactivity of the material, its oxygen buffering capability and thus its ability to act as a catalyst for both oxidation and reduction reactions. Ceria has important commercial utility in the areas of chemical mechanical polishing and planarization, catalytic converters and diesel oxidation catalysts, intermediate temperature solid oxide fuel cells and sensors. Its potential future uses include chemical looping combustion, photolytic and thermolytic water splitting for hydrogen production and as a therapeutic agent for the treatment of certain human diseases. We have seen that the method of synthesis, particle size, stabilizing corona, and purity dictate where it is used commercially. Finally, in regards to the prescient words of Dr. Feynman, we note that while there is indeed “plenty of room at the bottom”, there quite possibly exists an optimal nanoceria size of between 2–3 nm that provides maximal reactivity and thermodynamic stability.

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

          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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            The Hydrogen Economy

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              Electron localization determines defect formation on ceria substrates.

              The high performance of ceria (CeO2) as an oxygen buffer and active support for noble metals in catalysis relies on an efficient supply of lattice oxygen at reaction sites governed by oxygen vacancy formation. We used high-resolution scanning tunneling microscopy and density functional calculations to unravel the local structure of surface and subsurface oxygen vacancies on the (111) surface. Electrons left behind by released oxygen localize on cerium ions. Clusters of more than two vacancies exclusively expose these reduced cerium ions, primarily by including subsurface vacancies, which therefore play a crucial role in the process of vacancy cluster formation. These results have implications for our understanding of oxidation processes on reducible rare-earth oxides.
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                Author and article information

                Journal
                ESNNA4
                Environ. Sci.: Nano
                Environ. Sci.: Nano
                Royal Society of Chemistry (RSC)
                2051-8153
                2051-8161
                2014
                2014
                : 1
                : 5
                : 390-405
                Article
                10.1039/C4EN00079J
                aebc6a26-5946-4393-abca-5682d3056348
                © 2014
                History

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