Epitaxial Orientation Angle Tuned Disk-on-Rod Nanoheterostructures for Boosting Charge Transfer.

Controlling the compositions of Se(VI) and Te(VI) ions in a 2D disk on 1D structures of Sb(V) chalcogenides, disk-on-rod heterostructures having three different epitaxial angles with different surface facets are reported. Te injection temperature determined the composition, ensuring heterostructure formation with trigonal Sb2SexTe3-x disks on orthorhombic Sb2Se3 rods having orientation angles 180°, 135°, and 90°. The growth kinetics of disks connected at one/two heads of parent rods is manipulated using an Se precursor as a limiting reagent. Theoretical calculations established the energy minimization of different orientations, their possible formation, and suitability in energy transfer applications. Electrochemical measurements were also in agreement with theoretical calculations. Hence, this is a case study of advanced modular synthesis of disk-on-rod nanostructures, leading a step further in nanocrystal engineering for more desirable complex structures and their charge transfer property.

Au-Cu2-xTe Plasmonic Heteronanostructure Photoelectrocatalysts.

Semiconductor nanocrystals coupled with plasmonic Au nanoparticles have been widely studied as photoelectrocatalysts for solar water splitting. Among these, heterostructures of copper chalcogenides with Au remained a unique category for their dual plasmon character. However, while sulfides and selenides of copper have been extensively reported, heterostructures of copper tellurides with Au have not been explored. Herein, the plasmonic semiconductor Cu2-xTe disks grown on Au nanoparticles (disk-on-dot) were explored as efficient photoelectrocatalysts for hydrogen evolution reactions (HER). This has been successfully designed by growing Cu2-xTe disks on presynthesized Au nanoparticles under optimized reaction conditions. The resulting heterostructured nanocrystals acted as efficient photoelectrocatalysts for the H2 evolution reaction with a low Tafel slope and less cathodic overpotential in the presence of light. Details of their synthesis, characterization, optical properties, and electrocatalytic activities are studied and reported in this letter.

Facets and Defects in Perovskite Nanocrystals for Photocatalytic CO2 Reduction.

Light-emitting lead halide perovskite nanocrystals are typically obtained in a six-faceted cube shape. However, for applications such as catalysis, more active facets for the adsorption/desorption of reactants/products and the suppression of carrier recombination are essentially required. To meet these challenges, herein CsPbBr3 perovskite nanocrystals in cube and faceted noncube shapes were explored for photocatalytic reductions of CO2. Importantly, halide-deficient dim multifaceted noncube emitters having less than 1% photoluminescence quantum yields showed superior catalytic activity compared to that of bright halide-rich cube nanocrystals. Beyond these, hexapod-shaped nanocrystals were also explored, and these remained in an intermediate state. With the support of density functional theory, the adsorption and desorption probabilities of reactants/products on different facets were also calculated and correlated with experimental findings. These results indicated that facets and defects of perovskite nanocrystals are equally important for carrying out catalytic reactions.