Phosphorene, the 2D material derived from black phosphorus, has recently attracted a lot of interest for its properties, suitable for applications in materials science. The physical features and the prominent chemical reactivity on its surface render this nanolayered substrate particularly promising for electrical and optoelectronic applications. In addition, being a new potential ligand for metals, it opens the way for a new role of the inorganic chemistry in the 2D world, with special reference to the field of catalysis. The aim of this review is to summarize the state of the art in this subject and to present our most recent results in the preparation, functionalization, and use of phosphorene and its decorated derivatives. We discuss several key points, which are currently under investigation: the synthesis, the characterization by theoretical calculations, the high pressure behavior of black phosphorus, as well as its decoration with nanoparticles and encapsulation in polymers. Finally, device fabrication and electrical transport measurements are overviewed on the basis of recent literature and the new results collected in our laboratories.

Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) towards both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: i) the mixing of conventionally liquid-phase exfoliated bP (in DMSO) with PMMA solution; ii) the direct exfoliation of bP in a polymeric solution; iii) the in situ radical polymerization after exfoliating bP in the liquid monomer (methyl methacrylate, MMA). This last methodology concerns the preparation of stable suspensions of bPn-MMA by sonication-assisted liquid phase exfoliation (LPE) of bP in the presence of MMA followed by radical polymerization. The hybrids characteristics have been compared in order to evaluate the bP dispersion and the effectiveness of the bPn interfacial interactions with polymer chains aimed at their long-term environmental stabilization. The passivation of bPn results particularly effective when the hybrid material is prepared by in situ polymerization. By using this synthetic methodology, the nanoflakes, even if with a gradient of dispersion (size of aggregates), preserve their chemical structure from oxidation (as proved by both Raman and 31P-Solid State NMR studies) and are particularly stable to air and UV light exposure. The feasibility of this approach, capable of efficiently exfoliating bP while protecting the bPn, has been then verified by using different vinyl monomers (styrene and N-vinylpyrrolidone), thus obtaining hybrids where the nanoflakes are embedded in polymer matrices with a variety of intriguing thermal, mechanical and solubility characteristics.

Two antioxidant modified layered double hydroxides (AO-LDHs) were successfully prepared by the intercalation of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid (IrganoxCOOH) and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox) in the layered structure of LDH. It was found that by anchoring the phenolic moieties to the LDH layers the antioxidant power is retained in the case of Trolox, and even amplified in the case of IrganoxCOOH. A small amount of the two AO-LDHs was incorporated into poly(lactic acid), PLA, by solution mixing and melt extrusion. The thermo-oxidative stability of the composites was compared with that of the neat PLA and PLA containing free AOs. SEC analysis indicates that, after a controlled period of ageing, both the AO-LDHs protect the PLA from chain scission. The oxidation induction time (OIT, DSC) at 230 °C shows also the beneficial effects of the presence of the functional filler in the polymer matrix. Further, results from a preliminary migration test suggest that the AO species have a low tendency to migrate away from the AO-LDHs embedded in the polymer matrix thus keeping the AO protected inside the nanofiller layers thereby remaining active for a longer time