Climbing the Apex of the ORR Volcano Plot via Binuclear Site Construction: Electronic and Geometric Engineering,Journal of the American Chemical Society

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Climbing the Apex of the ORR Volcano Plot via Binuclear Site Construction: Electronic and Geometric Engineering
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-10-11 , DOI: 10.1021/jacs.9b08362
Meiling Xiao ₁ , Yongting Chen ₂ , Jianbing Zhu ₁ , Hao Zhang ₃ , Xiao Zhao ₄ , Liqin Gao ₁ , Xian Wang ₁ , Jin Zhao ₁ , Junjie Ge ₁ , Zheng Jiang _{3,

5} , Shengli Chen ₂ , Changpeng Liu ₁ , Wei Xing ₁

Affiliation

Great enthusiasms in single-atom catalysts (SACs) for the oxygen reduction reaction (ORR) are aroused by the discovery of M-Nx as a promising ORR catalysis center. However, the performance of SACs lags far behind that of state-of-the-art Pt due to the unsatisfactory adsorption-desorption behaviors of the reported catalytic centers. To address this issue, ra-tional manipulation of the active site configuration towards a well-managed energy level and geometric structure is ur-gently desired, yet still remains a challenge. Herein, we report a novel strategy to accomplish this task through the con-struction of an Fe-Co dual-atom centered site. A spontaneously absorbed electron-withdrawing OH ligand was proposed to act proactively as an energy level modifier to empower easy intermediate desorption, while the triangular Fe-Co-OH coordination facilitates O-O bond scission. Benefiting from these attributes, the as-constructed FeCoN5-OH site enables an ORR onset potential and half-wave potential of up to 1.02 and 0.86 V (vs. RHE) respectively, with an intrinsic activity over 20 times higher than the single-atom FeN4 site. Our finding not only opens up a novel strategy to tailor the electronic structure of an atomic site towards boosted activity, but also provides new insights into the fundamental understanding of diatomic sites for ORR electrocatalysis.

中文翻译：

通过双核站点建设攀登 ORR 火山地块的顶点：电子和几何工程

发现 M-Nx 作为有前景的 ORR 催化中心，激发了单原子催化剂（SAC）对氧还原反应（ORR）的极大热情。然而，由于报道的催化中心的吸附-解吸行为不令人满意，SACs 的性能远远落后于最先进的 Pt。为了解决这个问题，迫切需要合理操纵活性位点配置以达到管理良好的能级和几何结构，但仍然是一个挑战。在此，我们报告了一种通过构建 Fe-Co 双原子中心位点来完成此任务的新策略。提出了一种自发吸收的吸电子 OH 配体作为一种能级调节剂，使中间体易于解吸，而三角形 Fe-Co-OH 配位促进 OO 键断裂。受益于这些属性，所构建的 FeCoN5-OH 位点使 ORR 起始电位和半波电位分别高达 1.02 和 0.86 V（相对于 RHE），其内在活性比单原子高 20 倍以上FeN4 位点。我们的发现不仅开辟了一种新的策略来调整原子位点的电子结构以提高活性，而且还提供了对 ORR 电催化双原子位点的基本理解的新见解。

更新日期：2019-10-11

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