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The structures of vanadium oxide molecularly dispersed on oxide supports are unlike bulk phases, vanadium or its organometallic compounds. The dispersion of vanadium oxide triggers its exposure, which is the driving force for its applications in catalysis and surface science. The presence of an oxide support modifies the properties of the supported oxide, which in combination with coverage effect and the presence of additives helps creating a plethora of properties, with high relevance in catalysis, sensors and many other applications. This chapter presents a perspective essentially from the experience of the authors over the past 25 years. It addresses the nature of supported oxides and how these are affected by environmental conditions, loading and the presence of additives. Since environmental conditions may range from ambient hydrated to extreme pressure and atmospheres, the use of in-situ techniques is of paramount relevance to know the actual structure that supported vanadia species possess at given conditions. For catalyst materials, and functional materials in general, there is no point in knowing the structure at work if we do not know its performance. Among in-situ studies, operando methodology addresses this by providing simultaneous determination of material performance at genuine operation conditions and knowledge of its structure while working (“operando” in Latin). These aspects are considered from the perspective of catalytic application of supported vanadium oxides.

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