Understanding the effects of adduct functionalization on C60 nanocages for the hydrogen evolution reaction†

In this work, we use experimental and theoretical techniques to study the origin of the boosted hydrogen evolution reaction (HER) catalytic activity of two pyridyl-pyrrolidine functionalized C₆₀ fullerenes. Notably, the mono-(pyridyl-pyrrolidine) penta-adduct of C₆₀ has exhibited a remarkable HER catalytic activity as a metal-free catalyst, delivering an overpotential (η₁₀) of 75 mV vs. RHE and a very low onset potential of −45 mV vs. RHE. This work addresses fundamental questions about how functionalization on C₆₀ changes the electron density on fullerene cages for high-performance HER electrocatalysis.