By contrast, in the high pressure regime (6.8 and 10 GPa), the functional groups stay stably bonded to the surface for all the time of the unbiased MD simulation (5 ps). This occurs in all the configurations explored except for the meta systems simulated at 6.8 GPa, where the cleavage of the C-H and C-OCH 3 bonds and consequent formation of CH 3 OH at the interface is observed after 2 ps of two indipendent unbiased simulations. This indicates that high-pressure conditions thermodynamically favor the functionalization of BLG, compared to ambient ones. The molecular origin of such stabilization likely lies in the increase of the hydrophobic character of the methanol/BLG interface when increasing pressure. The functional OCH 3 group is located in the L1 layer and its first solvation shell is composed by both L1 (76.5 %) and L2 (23.5 %) methanol molecules (see Fig. in the S.I.) pointing their CH 3 moieties toward the OCH 3 functional group. In particular, we observe a decrease from 3.8 to 3.4 Å and from 7.4 to 6 Å in the case of the Methanol Carbon-Graphene distances for respectively the L1 and L2 methanol molecules (see Carbon density profiles and snapshot in Fig. -b in the S.I.). In addition, the interface molecular crowding in the high pressure regime provides a higher number of CH 3 moieties at the interface (14.5 methanol molecules at 6.8 GPa, vs 11.4 at ambient pressure) as can be appreciated in Table This results in a stronger and complete hydrophobic solvation of the OCH 3 groups that leads to a higher thermodynamic stabilization. However the functionalization of BLG with H and OCH 3 groups comes with a considerable enthalpic cost, with values of 236 and 288 kJ/mol, for 6.8 and 10 GPa respectively. Interestingly, these values remained consistent across all configurations tested (ortho, meta, para). In the next section we will characterize the kinetics of the BLG functionalization at high pressure by evaluating the free energy barriers with coordination based metadynamics.