Intrinsic Mechanical Effects on the Activation of Carbon Catalysts

The mechanical effects on carbon-based metal-free catalysts (C-MFCs) have rarely been explored, despite the global interest in C-MFCs as substitutes for noble metal catalysts. Stress is ubiquitous, whereas its dedicated study is severely restricted due to its frequent entanglement with other structural variables, such as dopants, defects, and interfaces in catalysis. Herein, we report a proof-of-concept study by establishing a platform to continuously apply strain to a highly oriented pyrolytic graphite (HOPG) lamina, simultaneously collecting electrochemical signals. Notably, we establish, for the first time, the correlation between the surface strain of graphitic carbon and its activation effect on the oxygen reduction reaction (ORR). Our results indicate that while in-plane and edge carbon sites in HOPG could not be further activated by applying tensile strain, a strong and repeatable dependence of catalytic activity on tensile strain was observed when the structure incorporated in-plane defects, leading to a significant ∼35.0% improvement in ORR current density with the application of ∼0.6% tensile strain. Density functional theory (DFT) simulations reveal that appropriate strain on specific defects can optimize the adsorption of reaction intermediates, and the Stone-Wales defect on graphene is correlated with the observed mechanical effect. This work elucidates fundamental principles of strain effects on the catalytic activity of graphitic carbon toward ORR and may lay the groundwork for the development of carbon-based mechano-electrocatalysis.