Among all the functional materials, ZnO plays an outstanding role in terms of chemical and physical properties, but also in terms of morphological variety and the number of reported synthesis approaches. Complex shapes and hierarchical architectures make ZnO a perfect example to study chemical and crystallization mechanisms. In this review article, we will discuss the nucleation and growth of ZnO nanostructures in liquid media by classical and non-classical (i.e., particle-based) crystallization pathways. We elaborate the chemical conditions and parameters that are responsible for the occurrence of one or the other pathway.

A detailed study is presented on the formation of MoO(2) nanoparticles from the dissolution of the precursor to the final rodlike product, with a focus on the exploration of the inorganic reaction occurring ahead of the nucleation step, and interplay between size and crystal structure of MoO(2). In situ X-ray absorption spectroscopy experiments show that the crystallization and the growth process of MoO(2) nanorods is initiated by rapid reduction of the MoO(2) Cl(2) precursor in benzyl alcohol and acetophenone. This reaction triggers the nucleation of 2 nm MoO(2) particles with spherical shape and hexagonal crystal structure. The transformation from spheres into rods emerges as a complex process driven by oriented attachment. High-resolution transmission electron microscopy and X-ray diffraction results provide evidence that the 2 nm particles first aggregate into 5-20 nm-large oriented assemblies. The increase in particle size induces the phase transition from hexagonal to the less symmetrical monoclinic crystal structure, and finally the transformation into rods. Is it shown that electrodes for lithium-ion batteries based on MoO(2) nanorods have a long-term cycling life. The specific discharge capacity even after 200 cycles at a discharge rate of 1 C is about 300 Ah kg(-1) .

Zinc oxide nanostructures are known to exist in a great variety of morphologies. However, the underlying mechanisms leading to these architectures are far from being fully understood. Here, we present a time dependent study of the generation of zinc oxide nanorods, which arrange into bundles with a fan- or bouquet-like structure, using the benzyl alcohol route. The structural evolution of the nanoparticles was monitored by electron microscopy techniques, whereas the progress of the chemical reaction was followed by quantification of the organic by-products using gas chromatography. With this study we give a detailed insight into the formation of the zinc oxide structures, which involves a complex pathway based on many in parallel occurring processes such as crystallization of primary particles, their oriented attachment and surface reconstruction inside the nanoparticulate agglomerates. However, in spite of such an intricate growth behavior, the ZnO nanostructures are surprisingly uniform in size and shape.

Crystalline ZnS and SnS(2) particles were synthesized by a modified benzyl alcohol route using benzyl mercaptan as solvent.

We present a detailed study on the nonaqueous synthesis of tungstite nanostructures with the focus on crystallization processes and the evolution of particle morphology. Time-dependent transmission electron microscopy (TEM) revealed a complex, particle-based crystallization mechanism involving first the formation of spherical and single-crystalline primary particles of 2-8 nm, which are cross-linked to large and unordered agglomerates, followed by their organization into rod-like structures of 40 × 200-400 nm. These rods undergo an internal ordering process, during which crystallographically oriented stacks of platelets develop. In situ small angle X-ray scattering (SAXS) experiments confirm this pathway of particle formation. The scattering intensity is dominated by the fast formation of rod-like particles, which cause an inter-platelet peak in the SAXS pattern with ongoing internal ordering. With continuous reaction time, the platelet stacks start to fall apart forming shorter assemblies of just a few platelets or even single platelets.