Noncovalent Immobilization of a Pyrene-Modified Cobalt Corrole on Carbon Supports for Enhanced Electrocatalytic Oxygen Reduction and Oxygen Evolution in Aqueous Solutions
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Abstract
Efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are the determinants of the realization of a hydrogen-based society, as sluggish OER and ORR are the bottlenecks for the production and utilization of H2, respectively. A Co complex of 5,15-bis(pentafluorophenyl)-10-(4)-(1-pyrenyl)phenylcorrole (1) bearing a pyrene substituent was synthesized. When it was immobilized on multiwalled carbon nanotubes (MWCNTs), the 1/MWCNT composite displayed very high electrocatalytic activity and durability for both OER and ORR in aqueous solutions: it catalyzed a direct four-electron reduction of O2 to H2O in 0.5 M H2SO4 with an onset potential of 0.75 V vs normal hydrogen electrode (NHE), and it catalyzed the oxidation of water to O2 in neutral aqueous solution with an onset potential of 1.15 V (vs NHE, η = 330 mV). Control studies using a Co complex of 5,10,15-tris(pentafluorophenyl)corrole (2) demonstrated that the enhanced catalytic performance of 1 was due to the strong noncovalent π–π interactions between its pyrene moiety and MWCNTs, which were considered to facilitate the fast electron transfer from the electrode to 1 and also to increase the adhesion of 1 on carbon supports. The noncovalent immobilization of molecular complexes on carbon supports through strong π–π interactions appears to be a simple and straightforward strategy to prepare highly efficient electrocatalytic materials.
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