The availability of high-quality colloidal nanosheets underpins a diverse range of applications and investigations into dimension-dependent physical properties. To facilitate this, synthetic methods that yield single-crystal colloidal nanosheets with regular shapes, uniform lateral dimensions, and tunable thicknesses are critically important. Most strategies that yield colloidal nanosheets achieve some, but not all, of these morphological characteristics. Here, we describe a synthetic pathway that generates colloidal nanosheets of SnSe with uniform lateral dimensions and tunable thicknesses. SnSe represents an excellent prototype system for studying the formation of colloidal nanosheets because of its layered crystal structure and the growing interest in its potential application as an absorption layer in low-cost photovoltaic devices. Freestanding colloidal SnSe nanosheets were synthesized by slowly heating a one-pot reaction mixture of SnCl(2), oleylamine, trioctylphosphine selenide (TOP-Se), and hexamethyldisilazane (HMDS) to 240 °C. The SnSe nanostructures adopt a uniform square-like morphology with lateral dimensions of approximately 500 nm × 500 nm, and the average nanosheet thicknesses can be tuned from approximately 10 to 40 nm by adjusting the concentrations of the SnCl(2) and TOP-Se reagents. Aliquot studies reveal fundamental insights into how the nanosheets form: they first "grow out" laterally via coalescence of individual nanoparticle building blocks to yield a single-crystal nanosheet template and then "grow up" vertically (through nanoparticle attachment to the nanosheet template) in a pseudo layer-by-layer fashion. Vertical growth is therefore limited, and can be controlled, by reagent concentration. Drop-cast films of the SnSe nanosheets are photoactive and have a bandgap of approximately 1 eV. These studies, demonstrated for SnSe but potentially applicable to other systems, establish a straightforward pathway for tuning the thicknesses of colloidal nanosheets while maintaining lateral uniformity.
Methane-producing hollow nanocubes: Hybrid CuO-TiO(2-x)N(x) hollow nanocubes have been synthesized by first depositing TiO(2) onto Cu(3)N nanocube templates, then heating in air to oxidize the Cu(3)N to CuO while concomitantly incorporating nitrogen into the TiO(2). The nanostructured CuO-TiO(2-x)N(x) material photocatalytically converts CO(2) into methane under solar irradiation.
The controlled growth of highly ordered, [211]-oriented FeOOH nanowire arrays on various substrates, such as Pt, W, Ti, and fluoride-doped tin oxide (FTO) glass, was achieved by a solvothermal method in aqueous acetonitrile solutions at 80À120 °C, following by annealing to form α-Fe 2 O 3 nanowires with their [110] direction perpendicular to the substrate. Adjusting the reaction pH and temperature enables control of the nanowire length. In particular, the pH has a dramatic effect on the nanowire growth, with low pH resulting in the growth of longer wires because of the acid-catalyzed hydrolysis of acetonitrile. Photoactive hematite was prepared by diffusing Ti or Sn into the nanowires during thermal annealing. Processing parameters that influenced the photoelectrochemical performance of these nanowire arrays, including the annealing regime, temperature, and length of nanowires, are discussed in detail. The Ti-and Sn-doped one-dimensional [110]-oriented α-Fe 2 O 3 nanowire arrays provide an effective pathway for electron transport, demonstrating increased photocurrents, up to 1.3 mA/cm 2 under air mass 1.5 global (AM 1.5G) illumination, in photoelectrochemical water oxidation.
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