To better understand the role nanoscale heterojunctions play in the photocatalytic generation of hydrogen, we have designed several model one-dimensional (1D) heterostructures based on CdSe nanowires (NWs). Specifically, CdSe/CdS core/shell NWs and Au nanoparticle (NP)-decorated core and core/shell NWs have been produced using facile solution chemistries. These systems enable us to explore sources for efficient charge separation and enhanced carrier lifetimes important to photocatalytic processes. We find that visible light H2 generation efficiencies in the produced hybrid 1D structures increase in the order CdSe < CdSe/Au NP < CdSe/CdS/Au NP < CdSe/CdS with a maximum H2 generation rate of 58.06 ± 3.59 μmol h(-1) g(-1) for CdSe/CdS core/shell NWs. This is 30 times larger than the activity of bare CdSe NWs. Using femtosecond transient differential absorption spectroscopy, we subsequently provide mechanistic insight into the role nanoscale heterojunctions play by directly monitoring charge flow and accumulation in these hybrid systems. In turn, we explain the observed trend in H2 generation rates with an important outcome being direct evidence for heterojunction-influenced charge transfer enhancements of relevant chemical reduction processes.

Semiconductor nanostructures produced by wet chemical synthesis are extremely heterogeneous, which makes single particle techniques a useful way to interrogate their properties. In this paper the ultrafast dynamics of single CdTe nanowires are studied by transient absorption microscopy. The wires have lengths of several micrometers and lateral dimensions on the order of 30 nm. The transient absorption traces show very fast decays, which are assigned to charge carrier trapping into surface defects. The time constants vary for different wires due to differences in the energetics and/or density of surface trap sites. Measurements performed at the band edge compared to the near-IR give slightly different time constants, implying that the dynamics for electron and hole trapping are different. The rate of charge carrier trapping was observed to slow down at high carrier densities, which was attributed to trap-state filling. Modulations due to the fundamental and first overtone of the acoustic breathing mode were also observed in the transient absorption traces. The quality factors for these modes were similar to those measured for metal nanostructures, and indicate a complex interaction with the environment.

High-quality compositionally tunable ternary PbSe(x)S(1-x) (x = 0.23, 0.39, 0.49, 0.68, and 0.90) nanowires (NWs) and their binary analogues have been grown using solution-liquid-solid growth with lead(II) diethyldithiocarbamate, Pb(S(2)CNEt(2))(2), and lead(II) imido(bis(selenodiisopropylphosphinate)), Pb((SeP(i)Pr(2))(2)N)(2), as single-source precursors. The alloyed nature of PbSe(x)S(1-x) wires was confirmed using ensemble X-ray diffraction and energy dispersive X-ray spectroscopy (EDXS). Single NW EDXS line scans taken along the length of individual wires show no compositional gradients. NW compositions were independently confirmed using inductively coupled plasma atomic emission spectroscopy. Slight stoichiometric deviations occur but never exceed 13.3% of the expected composition, based on the amount of introduced precursor. In all cases, resulting nanowires have been characterized using transmission electron microscopy. Mean diameters are between 9 and 15 nm with accompanying lengths that range from 4 to 10 μm. Associated selected area electron diffraction patterns indicate that the PbSe(x)S(1-x), PbSe, and PbS NWs all possess the same <002> growth direction, with diffraction patterns consistent with an underlying rock salt crystal structure.

Two-dimensional (2D) nanomaterials have recently received significant attention because of their attractiveness for use in many nanostructured devices. Layered transition-metal dichalcogenides are of particular interest because reducing their dimensionality causes changes in their already anisotropic physical and chemical properties. The present study describes the first bottom-up solution-phase synthesis of thin highly crystalline titanium disulfide (TiS2) nanosheets (NSs) using abundant low-cost molecular precursors. The obtained TiS2 NSs have average dimensions of ∼500 nm × 500 nm in the basal plane and have thicknesses of ∼5 nm. They exhibit broad absorption in the visible that tails out into the near-infrared. The obtained results demonstrate new opportunities in synthesizing low-dimensional 2D nanomaterials with potential use in various photochemical energy applications.

The electrostatic alignment and directed assembly of semiconductor nanowires into macroscopic, centimeter-long yarns is demonstrated. Different morphologies can be produced, including longitudinally segmented/graded yarns or mixed composition fibers. Nanowire yarns display long range photoconductivities and open up exciting opportunities for potential use in future nanowire-based textiles or in solar photovoltaics.