Theory Driven Design of Electrocatalysts for the Two Electron Oxygen Reduction Reaction Based on Dispersed Metal Phthalocyanines

The two-electron electrochemical reduction of oxygen is an appealing approach to produce hydrogen peroxide. Metal and heteroatom-doped carbon (M-X/C) materials have recently been recognized as compelling catalysts for this process, but their performance improvement is generally hindered by the ill-defined structures of active sites. Herein, we demonstrate a theory-driven design of catalysts for oxygen reduction reactions based on molecularly dispersed electrocatalysts (MDEs) with metal phthalocyanines on carbon nanotubes. Density functional theory calculations suggest that nickel phthalocyanine (NiPc) favors the formation of *H2O2 over *O, thus acting as a selective catalyst for peroxide production. NiPc MDE shows high peroxide yields of similar to 83%, superior to the aggregated NiPc and pyrolyzed Ni-N/C catalysts. The performance is further enhanced by the introduction of the cyano group (CN). NiPc-CN MDE exhibits similar to 92% peroxide yields and good stability. Our studies provide a new perspective for the development of heterogeneous electrocatalysts for hydrogen peroxide production from metal macrocyclic complexes.

Automated summary

In this study, a catalyst for oxygen reduction reactions based on metal phthalocyanine molecular electrocatalysts on carbon nanotubes was designed using density functional theory calculations. The introduction of a cyano group improved the selectivity and stability of the catalyst, resulting in a high yield of hydrogen peroxide.