Catalytic Light-Driven Generation of Hydrogen from Water by Iron Dithiolene Complexes.

The development of active, robust systems for light-driven hydrogen production from aqueous protons based on catalysts and light absorbers composed solely of earth abundant elements remains a challenge in the development of an artificial photosynthetic system for water splitting. Herein, we report the synthesis and characterization of four closely related Fe bis(benzenedithiolate) complexes that exhibit catalytic activity for hydrogen evolution when employed in systems with water-soluble CdSe QDs as photosensitizer and ascorbic acid as a sacrificial electron source under visible light irradiation (520 nm). The complex with the most electron-donating dithiolene ligand exhibits the highest activity, the overall order of activity correlating with the reduction potential of the formally Fe(III) dimeric dianions. Detailed studies of the effect of different capping agents and the extent of surface coverage of these capping agents on the CdSe QD surfaces reveal that they affect system activity and provide insight into the continued development of such systems containing QD light absorbers and molecular catalysts for H2 formation.

Super-resolution mapping of photogenerated electron and hole separation in single metal-semiconductor nanocatalysts.

Metal-semiconductor heterostructures are promising visible light photocatalysts for many chemical reactions. Here, we use high-resolution superlocalization imaging to reveal the nature and photocatalytic properties of the surface reactive sites on single Au-CdS hybrid nanocatalysts. We experimentally reveal two distinct, incident energy-dependent charge separation mechanisms that result in completely opposite photogenerated reactive sites (e(-) and h(+)) and divergent energy flows on the hybrid nanocatalysts. We find that plasmon-induced hot electrons in Au are injected into the conduction band of the CdS semiconductor nanorod. The specifically designed Au-tipped CdS heterostructures with a unique geometry (two Au nanoparticles at both ends of each CdS nanorod) provide more convincing high-resolution single-turnover mapping results and clearly prove the two charge separation mechanisms. Engineering the direction of energy flow at the nanoscale can provide an efficient way to overcome important challenges in photocatalysis, such as controlling catalytic activity and selectivity. These results bear enormous potential impact on the development of better visible light photocatalysts for solar-to-chemical energy conversion.

Molecular control of the nanoscale: effect of phosphine-chalcogenide reactivity on CdS-CdSe nanocrystal composition and morphology.

We demonstrate molecular control of nanoscale composition, alloying, and morphology (aspect ratio) in CdS-CdSe nanocrystal dots and rods by modulating the chemical reactivity of phosphine-chalcogenide precursors. Specific molecular precursors studied were sulfides and selenides of triphenylphosphite (TPP), diphenylpropylphosphine (DPP), tributylphosphine (TBP), trioctylphosphine (TOP), and hexaethylphosphorustriamide (HPT). Computational (DFT), NMR ((31)P and (77)Se), and high-temperature crossover studies unambiguously confirm a chemical bonding interaction between phosphorus and chalcogen atoms in all precursors. Phosphine−chalcogenide precursor reactivity increases in the order: HPTE < TOPE < TBPE < DPPE

Expanding the one-dimensional CdS-CdSe composition landscape: axially anisotropic CdS 1-x Se x nanorods.

We report the synthesis and characterization of CdS(1-x)Se(x) nanorods with axial anisotropy. These nanorods were synthesized via single injection of a mixture of trioctylphosphine sulfur and selenium precursors to a cadmium-phosphonate complex at high temperature. Transmission electron microscopy shows nanoparticle morphology changes with relative sulfur and selenium loading. When the synthetic selenium loading is between 5% and 10% of total chalcogenides, the nanorods exhibit pronounced axial anisotropy characterized by a thick "head" and a thin "tail". The nanorods' band gap red shifts with increasing selenium loading. X-ray diffraction reveals that CdS(1-x)Se(x) nanorods have a wurtzite crystal structure with a certain degree of alloying. High-resolution and energy-filtered transmission electron microscopy and energy-dispersive X-ray spectroscopy confirm the head of the anisotropic nanorods is rich in selenium, whereas the tail is rich in sulfur. Time evolution and mechanistic studies confirm the nanorods form by quick growth of the CdSe-rich head, followed by slow growth of the CdS-rich tail. Metal photodeposition reactions with 575 nm irradiation, which is mostly absorbed by the CdSe-rich segment, show effective electronic communication between the nanorod head and tail segments.