Metal nanostructures confined between sp2 hybridized 2D materials and their solid substrates are attracting attention for their potential application in new nanotechnologies, such as novel electronic and spintronic devices or nanoreactors. 2D-cover/ferromagnetic-metal/solid-substrate interface can stabilize ultrathin FM films with intriguing electronic structure and magnetic properties. In addition, atoms and molecules can be trapped at the interface between weakly interacting layers, such as h-BN or graphene and Pt(111), where they can further react. Model studies under well-defined conditions are valuable for understanding the fundamental aspects of the new phenomena under 2D covers. Herein, we will focus on thermally induced intercalation of Fe under single layer graphene  and mixed in-plane h-BN–graphene [2,3] heterostructures grown on Pt(111) and on the influence of oxygen on the intercalated system. Assets and benefits coming from advanced experimental techniques available at the Elettra synchrotron facility in Trieste will be presented. Basic processes, mechanisms, structural, chemical composition, and magnetic changes accompanying the intercalation process will be discussed on the basis of results obtained by synchrotron radiation experimental techniques, such as high-resolution X-ray photoemission spectroscopy (XPS), microscopy (PEEM), X-ray absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD) .
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