The analysis of the metadynamics bias in Fig. reveal free-energy barriers of approximately 150-200 kJ/mol, over twice the barrier observed under high-pressure conditions for BLGmethanol SV functionalization. The molecular origin of this significant barrier reduction in high pressure is likely due to the greater proximity of the first methanol layer to the BLG, which kinetically enhance the functionalization process (see density profiles in Fig. ). Our findings open up an interesting perspective on SV-BLG functionalization as a plausible mechanism for doping under high-pressure conditions. This mechanism could explains the observed pressure-induced doping of BLG in methanol, which begins in the early stages of compression and saturates around 2-3 GPa. This saturation is consistent with the leveling of the methanol-BLG distance, which stops decreasing beyond 2.9 GPa, as shown in our density profiles (Fig. ).