Fine Engineering of d-Orbital Vacancies of ZnN4 via High-Shell Metal and Nonmetal Single-Atoms for Efficient and Poisoning-Resistant ORR
At a Glance
Section titled āAt a Glanceā| Metadata | Details |
|---|---|
| Publication Date | 2024-11-08 |
| Journal | Nano Letters |
| Authors | Xiaoyuan Sun, Xinyi Li, Hong Huang, Wenting Lu, Xiaochun Xu |
| Institutions | Jilin University, State Key Laboratory of Inorganic Synthesis and Preparative Chemistry |
| Citations | 14 |
Abstract
Section titled āAbstractāAtomically dispersed metal-nitrogen-carbon (M-N-C) materials are active oxygen reduction reaction (ORR) catalysts. Among M-N-C catalysts, ZnN<sub>4</sub> single-atom catalysts (SACs) due to a nearly full 3d<sup>10</sup> electronic configuration insufficiently activate oxygen and display low ORR activity. To finely engineer d-orbital vacancies of ZnN<sub>4</sub>, we combine high-shell metal and nonmetal SAs as electronic regulators that are ZnN<sub>4</sub>Cl and carbon vacancy-hosted -Cl motifs, which show complementary electron-withdrawing capacities versus the ZnN<sub>4</sub>. Under that, the ZnN<sub>4</sub> exhibits significantly enhanced ORR activity with a half-wave potential (<i>E</i><sub>1/2</sub>) of 0.912 V<sub>RHE</sub> relative to the unmodified ZnN<sub>4</sub> (<i>E</i><sub>1/2</sub> = 0.822 V<sub>RHE</sub>) and simultaneously robust durability (negligible activity loss after 10,000 potential cycles). Particularly, the engineered ZnN<sub>4</sub> possesses high resistance to SCN<sup>-</sup> poisoning, which is rarely achieved among M-N-C SACs. Our works show that combining high-shell metal and nonmetal SAs can finely engineer d-orbital vacancies of metal centers to an optimal state, thereby intrinsically enhancing their catalytic performance.