Highly coordinative molecular cobalt-phthalocyanine electrocatalyst on an oxidized single-walled carbon nanotube for...

H₂O₂ production via the two-electron oxygen reduction reaction (2e^- ORR) offers a potential alternative to the current anthraquinone method owing to its efficiency and environmental friendliness. However, it is necessary to determine the structures of electrocatalysts with cost-effectiveness and high efficiency for future industrialization demand. Herein, a supramolecular catalyst composed of cobalt-phthalocyanine on a near-monodispersed and oxidized single-walled carbon nanotube (CoPc/o-SWCNT) was synthesized via a solution self-assembly method for catalyzing the 2e^- ORR for H₂O₂ electrosynthesis. Benefiting from the enhanced intermolecular interaction by introducing oxygen functional groups on o-SWCNTs, the oxidation states of single-atom Co sites were tuned via the formation of two extra Co-O bonds. Coupled with structural characterizations, density-functional theory (DFT) calculations reveal that the depressed d-band center of the Co site regulated by two axially-bridged O atoms gives rise to a suitable binding strength of oxygen intermediates (*OOH) to favor the 2e^- ORR. Thus, the CoPc-6wt%/o-SWCNT-2 catalyst with optimized synthetic parameters delivers competitive 2e^- ORR performance for H₂O₂ electrosynthesis in a neutral electrolyte (pH = 7), including enhanced H₂O₂ generation, satisfactory molar selectivity of ∼83-95% and long-period stability (75 h) in H-cell measurement. Moreover, it could also be boosted to show a high current of 45 mA cm^-2, recorded turnover frequency of 25.3 ± 0.5 s^-1 and maximum H₂O₂ production rate of 5.85 mol g^-1 h^-1 with a continuous H₂O₂ accumulation of 1.2 wt% in a flow-cell device, which outperformed most of the reported neutral-selective nonprecious metal single-atom catalysts.