ABSTRACT
Conductive metal oxides represent a new category of functional material with vital importance for many modern applications. The present work introduces a new conductive metal oxide V13 O16 , which is synthesized via a simplified photoelectrochemical procedure and decorated onto the semiconducting photocatalyst BiVO4 in controlled mass percentages ranging from 25% to 37%. Owing to its excellent conductivity and good compatibility with oxide materials, the metallic V13 O16 -decorated BiVO4 hybrid catalyst shows a high photocurrent density of 2.2 ± 0.2 mA cm-2 at 1.23 V versus reversible hydrogen electrode (RHE). Both experimental characterization and density functional theory calculations indicate that the superior photocurrent derives from enhanced charge separation and transfer, resulting from ohmic contact at the interface of mixed phases and superior electrical conductivity from V13 O16 . A Co-Pi coating on BiVO4 -V13 O16 further increases the photocurrent to 5.0 ± 0.5 mA cm-2 at 1.23 V versus RHE, which is among the highest reported for BiVO4 -based photoelectrodes. Surface photovoltage and transient photocurrent measurements suggest a charge-transfer model in which photocurrents are enhanced by improved surface passivation, although the barrier at the Co-Pi/electrolyte interface limits the charge transfer.
ABSTRACT
Highly oriented epitaxial rutile titanium dioxide (TiO2) nanowire arrays have been hydrothermally grown on polycrystalline TiO2 templates with their orientation dependent on the underlying TiO2 grain. Both the diameter and areal density of the nanowires were tuned by controlling the precursor concentration, and the template surface energy and roughness. Nanowire tip sharpness was influenced by precursor solubility and diffusivity. A new secondary ion mass spectrometer technique has been developed to install additional nucleation sites in single crystal TiO2 templates and the effect on nanowire growth was probed. Using the acquired TiO2 nanowire synthesis knowhow, an assortment of nanowire arrays were installed upon the surface of undoped TiO2 photo-electrodes and assessed for their photo-electrochemical water splitting performance. The key result obtained was that the presence of short and dispersed nanowire arrays significantly improved the photocurrent when the illumination intensity was increased from 100 to 200 mW cm-2. This is attributed to the alignment of the homoepitaxially grown nanowires to the [001] direction, which provides the fastest charge transport in TiO2 and an improved pathway for photo-holes to find water molecules and undertake oxidation. This result lays a foundation for achieving efficient water splitting under conditions of concentrated solar illumination.
ABSTRACT
Highly efficient visible-light catalysts are achieved through forming defect-pairs in TiO2 nanocrystals. This study therefore proposes that fine-tuning the chemical scheme consisting of charge-compensated defect-pairs in balanced concentrations is a key missing step for realizing outstanding photocatalytic performance. This research benefits photocatalytic applications and also provides new insight into the significance of defect chemistry for functionalizing materials.
ABSTRACT
The present work reports the tracer diffusion coefficient for (93)Nb in rutile TiO(2) single crystals using secondary ion mass spectrometry (SIMS). The determined tracer diffusion coefficient exhibited the following temperature dependence in air ( p(O2) = 21 kPa) over the range 1073-1573 K: D93(Nb) = (4.7 m2 s(-1))x10(-7+/-0.4) exp ((-244 +/- 9 kJ mol-1)/RT) Through comparison to the self-diffusion of (44)Ti in rutile TiO(2), (93)Nb is interpreted to diffuse via the interstitialcy mechanism. The obtained tracer diffusion data are useful for ensuring compositional control during the processing of Nb-doped TiO(2)-based semiconductors using solid-state reactions between Nb(2)O(5) and TiO(2).
