Structural transitions at the bilayer graphene–methanol interface from ab initio molecular dynamics

The precise tailoring of the atomic architecture of 2D carbon-based materials holds significant promise for advancing technologies in electronics, spintronics, and energy storage by modulating their physical properties. High-pressure conditions can facilitate the synthesis of complex materials derived from multi-layer graphene, often through chemical transformations at interfaces with pressure-transmitting media such as water or alcohol. However, experimental characterization of molecular-scale mechanisms at these interfaces presents significant challenges. Similarly, the high computational cost of ab initio simulations has so far restricted computational studies to simplified models, often failing to capture the complexity and finite-temperature effects of such systems. In this work, we present the first extensive computational study of realistic bilayer graphene-methanol interfaces under high-pressure and finite-temperature conditions. Utilizing state-of-the-art enhanced sampling techniques and topological electronic descriptors, our simulations provide fundamental insights into the structural, electronic, and reactivity properties of these interfaces. Specifically, we reveal the role of carbon defects in catalyzing sp3 functionalization processes, addressing key questions raised by previous experimental findings. This work opens new avenues for understanding and designing carbon-based materials under extreme conditions.