Tungsten and molybdenum oxide nanostructures: two-dimensional layers and nanoclusters

W- and Mo-oxides form an interesting class of materials, featuring structural complexities, stoichiometric flexibility, and versatile physical and chemical properties that render them attractive for many applications in diverse fields of nanotechnologies. In nanostructured form, novel properties and functionalities emerge as a result of quantum size and confinement effects. In this topical review, W- and Mo-oxide nanosystems are examined with particular emphasis on two-dimensional (2D) layers and small molecular-type clusters. We focus on the epitaxial growth of 2D layers on metal single crystal surfaces and investigate their novel geometries and structures by a surface science approach. The coupling between the oxide overlayer and the metal substrate surface is a decisive element in the formation of the oxide structures and interfacial strain and charge transfer are shown to determine the lowest energy structures. Atomic structure models as determined by density functional theory (DFT) simulations are reported and discussed for various interface situations, with strong and weak coupling. Free-standing (quasi-)2D oxide layers, so-called oxide nanosheets, are attracting a growing interest recently in the applied research community because of their easy synthesis via wet-chemical routes. Although they consist typically of several atomic layers thick-not always homogeneous-platelet systems, their quasi-2D character induces a number of features that make them attractive for optoelectronic, sensor or biotechnological device applications. A brief account of recently published preparation procedures of W- and Mo-oxide nanosheets and some prototypical examples of proof of concept applications are reported here. (MO₃)₃(M = W, Mo) clusters can be generated in the gas phase in nearly monodisperse form by a simple vacuum sublimation technique. These clusters, interesting molecular-type structures by their own account, can be deposited on a solid surface in a controlled way and be condensed into 2D W- and Mo-oxide layers; solid-state chemical reactions with pre-deposited surface oxide layers to form 2D ternary oxide compounds (tungstates, molybdates) have also been reported. The clusters have been proposed as model systems for molecular studies of reactive centres in catalytic reactions. Studies of the catalysis of (MO₃)₃clusters in unsupported and supported forms, using the conversion of alcohols as model reactions, are discussed. Finally, we close with a brief outlook of future perspectives.