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Endowing metal-free graphitic carbon electrodes with high electrocatalytic reactivity is a field of intense research, but remains elusive. Here, we introduce a prototypical edge-plane-site-specific engineering strategy on “herringbone” multi-walled carbon nanotubes by performing an intercalation-exfoliation and truncation process in molten inorganic salts. Controllable synthesis of the target H-MWCNTs-MS with fully exposed edge-plane sites on both the outer surface and inner channels was demonstrated. in-situinfrared spectroscopic study supports the theoretically energetic “edge-state” and identifies the reconstructed ketone/carboxyl-terminated edge sites under oxygen evolution reaction (OER) conditions. These oxygenated edge-plane sites boost charge redistribution and interlayer coupling, which essentially govern the synergistic catalysis, as evidenced by combined theoretical, electrokinetic, and H/D isotopic studies. Benefiting from the dense reactive sites and efficient electron tunneling, the H-MWCNTs-MS demonstrated impressive OER activity with an overpotential of 236 mV at a current density of 10 mA cm−2in alkaline media, outperforming most state-of-the-art metal-free electrocatalysts reported to date. Furthermore, the catalyst displayed no noticeable degradation during 100 h of operation, indicating its potential for practical applications.

Imine-linked covalent organic frameworks (COFs) provide distinctive prospects for promoting photocatalytic H2O2production, yet the intricate involvement of imine-derived linkages chemistry under light irradiation remains incompletely elucidated. Here, imine-linked COF-LZU1 demonstrates a visible light-driven H2O2evolution rate of 387 ​μmol ​g−1 ​h−1, particularly, negligible dependence on the sacrificial agents. By virtue of electron paramagnetic spectroscopy and solid-state nuclear magnetic resonance, we experimentally tracked the structure evolution and identified its autooxidation to Wurster's salt mimics under the photocatalytic conditioning. This finding coincides with the radical anion ·O2−governed reaction pathway and is further rationalized with additional theoretical calculations. This study provides insights into both photophysical/photochemical aspects over the imine-linkage structure.