Key Laboratory of Special Functional Materials for Ecological Environment and Information, Ministry of Education, School of Material Science and Engineering, Hebei University of Technology, Tianjin, 300130, P. R. China.
Department of Physics and Astronomy, University of California, Irvine, CA, 92697, USA.
Small. 2023 Feb;19(8):e2206071. doi: 10.1002/smll.202206071. Epub 2022 Dec 11.
Atomically dispersed nitrogen-coordinated 3d transition-metal site on carbon support (M-NC) are promising alternatives to Pt group metal-based catalysts toward oxygen reduction reaction (ORR). However, despite the excellent activities of most of M-NC catalysts, such as Fe-NC, Co-NC et al., their durability is far from satisfactory due to Fenton reaction. Herein, this work reports a novel Si-doped Ni-NC catalyst (Ni-SiNC) that possesses high activity and excellent stability. X-ray absorption fine structure and aberration-corrected transmission electron microscopy uncover that the single-atom Ni site is coordinated with one Si atom and three N atoms, constructing Ni-Si N moiety. The Ni-SiNC catalyst exhibits a half-wave potential (E ) of 0.866 V versus RHE, with a distinguished long-term durability in alkaline media of only 10 mV negative shift in E after 35 000 cycles, which is also validated in Zn-air battery. Density functional theory calculations reveal that the Ni-Si N moiety facilitates ORR kinetics through optimizing the adsorption of intermediates.
担载在碳载体上的原子分散氮配位 3d 过渡金属位点（M-NC）是替代铂族金属基催化剂用于氧还原反应（ORR）的有前途的选择。然而，尽管大多数 M-NC 催化剂（如 Fe-NC、Co-NC 等）具有优异的活性，但由于芬顿反应，其耐久性远不能令人满意。在此，本工作报道了一种新型的硅掺杂镍-氮配位催化剂（Ni-SiNC），它具有高活性和优异的稳定性。X 射线吸收精细结构和像差校正透射电子显微镜揭示了单原子 Ni 位点与一个 Si 原子和三个 N 原子配位，构建了 Ni-Si N 部分。该 Ni-SiNC 催化剂在碱性介质中的半波电位（E ）为 0.866 V 相对于 RHE，在 35000 次循环后仅负移 10 mV，具有出色的长期耐久性，在锌-空气电池中也得到了验证。密度泛函理论计算表明，Ni-Si N 部分通过优化中间体的吸附来促进 ORR 动力学。
