Organometallic Synthesis, Structure Determination, Shape Evolution, and Formation Mechanism of Hexapod-like Ternary PbSexS1?x Nanostructures with Tunable Compositions

摘要

The fabrication of hexapod-like ternary PbSe_xS_(1?x) nanostructures has been reported via an alternative organometallic route from reaction of Pb(II) salt with triphenylphosphine selenide (Ph_3PSe) and dibenzyl disulfide (DBDS) in dibenzylamine (DBA) with addition of oleic acid (OA) at 260 ℃. The shape, structure, and composition of the nanostructured hexapods are investigated and determined by techniques of XRD, SEM, TEM, Raman, HRTEM, SAED, XPS, EDX, and HAADF-STEM, and the obtained ternary nanostructured hexapods are of typical rock salt phase with Pbrich features without phase separation, and their compositions could be systematically regulated by facile variations of reaction parameters. Investigations reveal that the successful fabrication of the ternary hexapods with tunable compositions is resulted from the effective selection of Se and S sources of Ph_3PSe and DBDS that have similar reactivity in the current reaction system along with small lattice mismatch between the two end members of PbSe and PbS. Generally, the relations between the composition and lattice parameters for the ternary nanostructures obtained in DBA with varied addition of OA exhibit linear slops that are consistent well with Vegard’s law. Interestingly, intensive investigations show that the nanostructures are mainly gradiently alloyed nanostructures with somewhat chalcogen?element segregations or disorders rather than homogeneously alloyed solid-state solutions due to kinetic limitation for short reaction time even though thermodynamics is feasible in the system, and also, high concentration of S element in the feedstocks tends to relative high density of disorders in the ternary nanostructures. Based on the revealing of the formation mechanism for the nanostructures with varied microstructures, the ternary PbSe_xS_(1?x) hexapods can be tuned from gradient alloys with segregations to approximately homogeneous via enlongating reaction time. In addition, the photolysis of the nanostructures to lead oxysulfate and oxyselenate species is evidenced at ambient condition via Raman detection although they are stable at ?190 °C.