Mechanisms of Nanoscroll Formation and Particle Encapsulation in Janus MXenes

Abstract

Morphology transfer of 2D Janus MXenes into nanoscrolls unlocks unusual properties. Although a scalable synthesis route has been experimentally verified, the atomistic mechanism underlying nanoscroll formation remains poorly understood. We use large-scale reactive molecular dynamics simulations, validated against density functional theory (DFT) and experimental structural and elastic properties, to investigate stability and quantify the driving forces and geometry governing nanoscroll formation in three Janus MXenes, (Tx)Ti2C(Ty), where (Tx) and (Ty) denote the bottom and top surface terminations among bare (-b), -O, and -OH. Both square and infinitely wide flakes with lengths ranging from 10 to over 120 nm are simulated. We find that 1-7% lattice-induced strain generates a bending moment in these structures. The sheet scrolls, curves, or forms a nanotube depending on the resulting curvature and initial sheet size. For MXenes with an initial length of 120 nm, multiwalled nanoscrolls form with interlayer distances of around 0.7 nm and inner diameters of about 7 nm for (O)Ti2C(OH) and (b)Ti2C(OH), whereas (b)Ti2C(O) instead produces a much larger interlayer distance of around 1.7 nm and an inner diameter exceeding 20 nm. We show that spontaneous scrolling of a Janus MXene in the presence of an anchored nanoparticle produces a core@shell composite, in which the particle locally deforms the nanoscroll and widens the interlayer channels. This locally tunable, enlarged interlayer spacing offers a promising design route for MXene-based energy-storage electrodes. However, our simulations reveal H2 gas release during encapsulation, which promotes nanobubble formation that can reduce battery life.