A Single-Atom Iridium Heterogeneous Catalyst in Oxygen Reduction Reaction

摘要

Combining the advantages of homogeneous and heterogeneous catalysts, single-atom catalysts (SACs) are bringing new opportunities to revolutionize ORR catalysis in terms of cost, activity and durability. However, the lack of high-performance SACs as well as the fundamental understanding of their unique catalytic mechanisms call for serious advances in this field. Herein, for the first time, we develop an Ir-N-C single-atom catalyst (Ir-SAC) which mimics homogeneous iridium porphyrins for high-efficiency ORR catalysis. In accordance with theoretical predictions, the as-developed Ir-SAC exhibits orders of magnitude higher ORR activity than iridium nanoparticles with a record-high turnover frequency (TOF) of 24.3e(-) site(-1)s(-1) at 0.85V vs. RHE) and an impressive mass activity of 12.2Amg(Ir)(-1), which far outperforms the previously reported SACs and commercial Pt/C. Atomic structural characterizations and density functional theory calculations reveal that the high activity of Ir-SAC is attributed to the moderate adsorption energy of reaction intermediates on the mononuclear iridium ion coordinated with four nitrogen atom sites.