Nanometal materials play very important roles in solar-to-chemical energy conversion due to their unique catalytic and optical characteristics. They have found wide applications from semiconductor photocatalysis to rapidly growing surface plasmon-mediated heterogeneous catalysis. The recent research achievements of nanometals are reviewed here, with regard to applications in semiconductor photocatalysis, plasmonic photocatalysis, and plasmonic photo-thermocatalysis. As the first important topic discussed here, the latest progress in the design of nanometal cocatalysts and their applications in semiconductor photocatalysis are introduced. Then, plasmonic photocatalysis and plasmonic photo-thermocatalysis are discussed. A better understanding of electron-driven and temperature-driven catalytic behaviors over plasmonic nanometals is helpful to bridge the present gap between the communities of photocatalysis and conventional catalysis controlled by temperature. The objective here is to provide instructive information on how to take the advantages of the unique functions of nanometals in different types of catalytic processes to improve the efficiency of solar-energy utilization for more practical artificial photosynthesis.
In this study, for the first time, {111} facet exposed
anatase
TiO2 single crystals are prepared via both F– and ammonia as the capping reagents. In comparison with the most
investigated {001}, {010}, and {101} facets for anatase TiO2, the density functional theory (DFT) calculations predict that {111}
facet owns a much higher surface energy of 1.61 J/m2, which
is partially attributed to the large percentage of undercoordinated
Ti atoms and O atoms existed on the {111} surface. These undercoordinated
atoms can act as active sites in the photoreaction. Experimentally,
it is revealed that this material exhibits the superior electronic
band structure which can produce more reductive electrons in the photocatalytic
reaction than those of the TiO2 samples exposed with majority
{010}, {101}, and {001} facets. More importantly, we demonstrate that
this material is an excellent photocatalyst with much higher photocatalytic
activity (405.2 μmol h–1), about 5, 9, and
13 times that of the TiO2 sample exposed with dominant
{010}, {101}, and {001} facets, respectively. Both the superior surface
atomic structure and electronic band structure significantly contribute
to the enhanced photocatalytic activity. This work exemplifies that
the surface engineering of semiconductors is one of the most effective
strategies to achieve advanced and excellent performance over photofunctional
materials for solar energy conversion.
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