Second-shell modulation on porphyrin-like Pt single atom catalysts for boosting oxygen reduction reaction

The first coordination shell is considered crucial in determining the performance of single atom catalysts (SACs), but the significance of the second coordination shell has been overlooked. In this study, we developed a post-doping strategy to realize predictable and controlled modulation on the second coordination shell. By incorporating a P atom into the second coordination shell of a porphyrin-like Pt SAC, the charge density at the Fermi level of Pt single atom increases, enhancing its intrinsic activity. Moreover, the P atom shows stronger adsorption towards large size anions (ClO₄⁻) than Pt atoms, preventing the Pt site poisoning in acid. As a result, the Pt-N₄P-C catalyst exhibits significantly higher activity than the Pt-N₄-C catalyst. It even outperforms commercial Pt/C (20 wt% Pt) with a Pt content of only 0.22 wt% in both alkaline and acidic solutions. This work indicates the second coordination shell modulation also greatly impacts the performance of SACs.