Polymer-based black phosphorus (bP) hybrid materials by in situ radical polymerization: an effective tool to exfoliate bP and stabilize bP nanoflakes

TL;DR

This paper presents a novel polymer-based hybrid material with exfoliated black phosphorus nanoflakes that are significantly stabilized against environmental degradation through in situ radical polymerization, enhancing their practical applicability.

Contribution

The study introduces a new in situ polymerization method to stabilize black phosphorus nanoflakes, improving their resistance to air and UV exposure compared to previous approaches.

Findings

Hybrid materials show enhanced stability against oxidation and environmental factors.

In situ polymerization preserves the chemical structure of bP nanoflakes.

Effective stabilization achieved even with dispersion gradients.

Abstract

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.