BiVO4 has become the top-performing semiconductor among photoanodes for photoelectrochemical water oxidation. However, BiVO4 photoanodes are still limited to a fraction of the theoretically possible photocurrent at low applied voltages because of modest charge transport properties and a trade-off between light absorption and charge separation efficiencies. Here, we investigate photoanodes composed of thin layers of BiVO4 coated onto Sb-doped SnO2 (Sb:SnO2) nanorod-arrays (Sb:SnO2/BiVO4 NRAs) and demonstrate a high value for the product of light absorption and charge separation efficiencies (ηabs × ηsep) of ∼51% at an applied voltage of 0.6 V versus the reversible hydrogen electrode, as determined by integration of the quantum efficiency over the standard AM 1.5G spectrum. To the best of our knowledge, this is one of the highest ηabs × ηsep efficiencies achieved to date at this voltage for nanowire-core/BiVO4-shell photoanodes. Moreover, although WO3 has recently been extensively studied as a core nanowire material for core/shell BiVO4 photoanodes, the Sb:SnO2/BiVO4 NRAs generate larger photocurrents, especially at low applied voltages. In addition, we present control experiments on planar Sb:SnO2/BiVO4 and WO3/BiVO4 heterojunctions, which indicate that Sb:SnO2 is more favorable as a core material. These results indicate that integration of Sb:SnO2 nanorod cores with other successful strategies such as doping and coating with oxygen evolution catalysts can move the performance of BiVO4 and related semiconductors closer to their theoretical potential.
The microscopic interactions at heterojunctions formed between cleaned surfaces of InSb and CdTe have been investigated by low-energy electron diffraction and soft x-ray photoelectron spectroscopy. Layers of CdTe have been deposited on 1×1 (110) cleaved InSb and on c(2×8) (100) sputter cleaned and annealed surfaces, for various substrate temperatures. The valence-band offset has been measured and compared with theoretical predictions for layers deposited on room-temperature substrates. For layers deposited onto substrates at elevated temperatures typical of those employed in molecular beam epitaxial growth, the interface is complex and consists of a region rich in indium and tellurium, presumed to be indium telluride. The thickness of this layer is temperature dependent and may be several tens of angstroms.
Mo17O47 nanowire-arrays are promising active materials and electrically-conductive supports for batteries and other devices. While high surface area resulting from long, thin, densely packed nanowires generally leads to improved performance in a wide variety of applications, the Mo17O47 nanowire-arrays synthesized previously by electrically-heated chemical vapor deposition under vacuum conditions were relatively thick and short. Here, we demonstrate a method to grow significantly thinner and longer, densely packed, high-purity Mo17O47 nanowire-arrays with diameters of 20–60 nm and lengths of 4–6 μm on metal foil substrates using rapid atmospheric flame vapor deposition without any chamber or walls. The atmospheric pressure and 1000 °C evaporation temperature resulted in smaller diameters, longer lengths and order-of-magnitude faster growth rate than previously demonstrated. As explained by kinetic and thermodynamic calculations, the selective synthesis of high-purity Mo17O47 nanowires is achieved due to low oxygen partial pressure in the flame products as a result of the high ratio of fuel to oxidizer supplied to the flame, which enables the correct ratio of MoO2 and MoO3 vapor concentrations for the growth of Mo17O47. This flame synthesis method is therefore a promising route for the growth of composition-controlled one-dimensional metal oxide nanomaterials for many applications.
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