Metal sulphides, and in particular transition metal sulphide colloids, are a broad, versatile and exciting class of inorganic compounds which deserve growing interest and attention ascribable to the functional properties that many of them display. With respect to their oxide homologues, however, they are characterised by noticeably different chemical, structural and hence functional features. Their potential applications span several fields, and in many of the foreseen applications (e.g., in bioimaging and related fields), the achievement of stable colloidal suspensions of metal sulphides is highly desirable or either an unavoidable requirement to be met. To this aim, robust functionalisation strategies should be devised, which however are, with respect to metal or metal oxides colloids, much more challenging. This has to be ascribed, inter alia, also to the still limited knowledge of the sulphides surface chemistry, particularly when comparing it to the better established, though multifaceted, oxide surface chemistry. A ground-breaking endeavour in this field is hence the detailed understanding of the nature of the complex surface chemistry of transition metal sulphides, which ideally requires an integrated experimental and modelling approach. In this review, an overview of the state-of-the-art on the existing examples of functionalisation of transition metal sulphides is provided, also by focusing on selected case studies, exemplifying the manifold nature of this class of binary inorganic compounds.
Atomic- and nanometer-scale features of nanomaterials have a strong influence on their chemical and physical properties and a detailed description of these elements is a crucial step in their characterization. Total scattering methods, in real and reciprocal spaces, have been established as fundamental techniques to retrieve this information. Although the impact of microstructural features, such as defectiveness of different kinds, has been extensively studied in reciprocal space, disentangling these effects from size- and morphology-induced properties, upon downsizing, is not a trivial task. Additionally, once the experimental pattern is Fourier transformed to calculate the pair distribution function, the direct fingerprint of structural and microstructural features is severely lost and no modification of the histogram of interatomic distances derived therefrom is clearly discussed nor considered in the currently available protocols. Hereby, starting from atomistic models of a prototypical system (cadmium selenide), we simulate multiple effects on the atomic pair distribution function, obtained from reciprocal space patterns computed through the Debye scattering equation. Size and size dispersion effects, as well as different structures, morphologies, and their interplay with several kinds of planar defects, are explored, aiming at identifying the main (measurable and informative) fingerprints of these features on the total scattering pattern in real and reciprocal spaces, highlighting how, and how much, they become evident when comparing different cases. The results shown herein have general validity and, as such, can be further extended to other classes of nanomaterials.
Crystalline spinel quaternary ferrites M x Zn 1−x Fe 2 O 4 (M = Co, Ni) were synthesised through two synthetic routes: conventional batch and continuous flow hydrothermal synthesis.