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Interfacing topological insulators (TI) with magnetic materials enables accessing quantum effects for advanced devices. The synthesis of such heterostructures faces challenges due to interlaying mixing and the often-complex multicomponent materials required to combine the desired properties. An alternative synthesis to direct growth is the modification of 2D materials by topotactic reactions to introduce new functionalities into pre-formed single or few-component 2D sheets. Here, the self-formation of bismuthene (a bilayer of Bi; Bi2) is utilized by thermal decomposition of Bi2Te3 as a platform to create novel 2D overlayers on the TI- substrate. Specifically, the Bi2 layer is modified by reacting it with vapor deposited Mn in an attempt to induce magnetic properties. Scanning tunneling microscopy indicates that the Mn modified surface remains in a planar 2D layer, indicating the formation of an ordered Mn-rich surface layer. Density functional theory (DFT) is used to develop models of both the Bi-rich Bi2Te3 surface as well as their subsequent Mn-modified structure. The DFT models indicate the possibility of magnetic ordering of the high spin Mn2+ ions. The successful synthesis of planar MnBi alloys on a van der Waals material illustrates topotactic reactions as an alternative for creating novel layered heterostructures. 

The Pt-Te compositional phase diagram consists of at least three different compositional line phases (PtTe2, Pt3Te4, and Pt2Te2) that can be described as layered van der Waals materials. This presents challenges in controlling the composition of ultrathin Pt-telluride 2D materials by physical vapor deposition methods. Here we show by temperature programmed synchrotron photoemission spectroscopy that the different phases have varying thermal stability in vacuum. This enables the synthesis of these materials by preparation of PtTe2 films at low growth temperatures and subsequent vacuum annealing to ~ 350 ˚C for Pt3Te4, or ~400 ˚C for Pt2Te2. Such prepared phases are characterized by high resolution core level spectroscopy to provide reference spectra for these materials. Moreover, the chemical stability of these materials was tested by exposure to oxygen and air. Even after prolonged air exposure only the surface Te layer was modified by oxygen chemical bonds that caused a 3-eV shift to higher binding energy of the Te-3d core levels. However, these oxygen species could be desorbed by vacuum annealing at 280 ˚C and pristine Pt-telluride samples can be re-established. This shows the excellent chemical stability of these materials, important for practical applications. 

The adsorption and dissociation of water molecules on two-dimensional transition metal dichalcogenides (TMDs) is expected to be dominated by point defects, such as vacancies, and edges. At the same time, the role of grain boundaries, and particularly, mirror twinboundaries (MTBs), whose concentration in TMDs can be quite high, is not fully understood. Using density functional theory calculations, we investigate the interaction of water, hydroxyl groups, as well as oxygen and hydrogen molecules with MoSe 2 monolayers when MTBs of various types are present. We show that the adsorption of all species on MTBs is energetically favorable as compared to that on the basal plane of pristine MoSe 2 , but the interaction with Se vacancies is stronger. We further assess the energetics of various surface chemical reactions involving oxygen and hydrogen atoms. Our results indicate that water dissociation on the basal plane should be dominated by vacancies even when MTBs are present, but they facilitate water clustering through hydroxyl groups at MTBs, which can anchor water molecules and give rise to the decoration of MTBs with water clusters. Also, the presence of MTBs affects oxygen reduction reaction (ORR) on the MoSe 2 monolayer. Unlike Se vacancies which inhibit ORR due to a high overpotential, it is found that the ORR process on MTBs is more efficient, indicating their important role in the catalytic activity of MoSe 2 monolayer and likely other TMDs.