铽诱导的钴价带变窄促进电催化氧还原,Energy & Environmental Science

当前位置： X-MOL 学术 › Energy Environ. Sci. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

铽诱导的钴价带变窄促进电催化氧还原
Energy & Environmental Science ( IF 32.4 ) Pub Date : 2023-10-10 , DOI: 10.1039/d3ee02503a
Xuan Wang ₁ , Juan Zhang ₁ , Pu Wang ₁ , Liangcheng Li ₁ , Huiyu Wang ₁ , Dongmei Sun ₁ , Yafei Li ₁ , Yawen Tang ₁ , Xue Feng Lu ₂ , Yu Wang ₁ , Gengtao Fu ₁

Affiliation

稀土（RE）基材料正在发展成为电催化氧还原反应（ORR）的有前景的范例，以引领能源转换技术的实际应用。然而，对 RE 在增强 ORR 中的催化作用的系统理解仍然有限。_{在此，我们开发了一种新型稀土基催化剂，由原子 Co 物种与 Tb 2} O ₃ (Co@Tb ₂ O ₃ )耦合组成，以揭示稀土在增强 ORR 性能中的作用。Co@Tb ₂ O ₃具有令人满意的 ORR 活性，起始电位和半波电位分别为 1.02 V _RHE和 0.85 V _RHE，优于 Pt/C 基准和许多报道的钴基催化剂。准操作X 射线光电子能谱显示 Co 2p 和 Tb 3d/4d 的结合能和半峰全宽与电势相关的变化，证明了 ORR 过程中氧中间体的成功覆盖和转化。理论计算表明，Co@Tb ₂ O ₃中构建的[Co–O–Tb]单元位点通过Co 3d–O 2p–Tb 4f 的梯度轨道耦合赋予Co 3d较窄的能带和适当的能带位置。[Co-O-Tb]单元位点中的这种窄带行为使得Co位点与氧中间体之间的相互作用以理想的σ/π键混合类型的形式存在，这提供了氧中间体灵活的结合强度，从而打破了*OOH 和*OH 的缩放关系更接近最佳条件。我们相信这项工作将为高效稀土基ORR材料的设计建立新的理解。

"点击查看英文标题和摘要"

Terbium-induced cobalt valence-band narrowing boosts electrocatalytic oxygen reduction

Rare-earth (RE)-based materials are evolving as a promising paradigm for the electrocatalytic oxygen reduction reaction (ORR) to lead the practical application in energy conversion technologies. However, the systematic comprehension of the catalytic role of RE in the enhanced ORR is still limited. Herein, we develop a novel RE-based catalyst consisting of atomic Co species coupled with Tb₂O₃ (Co@Tb₂O₃) to unveil the role of RE in enhanced ORR performance. Co@Tb₂O₃ delivers satisfactory ORR activity with an onset potential and half-wave potential of 1.02 V_RHE and 0.85 V_RHE, respectively, outperforming the Pt/C benchmark and many reported Co-based catalysts. Quasi-operando X-ray photoemission spectroscopy exhibits potential-dependent shifts of binding energy and full width at half maximum for Co 2p and Tb 3d/4d, demonstrating the successful coverage and transformation of oxygen intermediates during the ORR. Theoretical calculations uncover that the constructed [Co–O–Tb] unit site in Co@Tb₂O₃ endows Co 3d with a narrow band and appropriate band location via the gradient orbital coupling of Co 3d–O 2p–Tb 4f. Such narrow-band behavior in the [Co–O–Tb] unit site makes the interaction between the Co site and oxygen intermediates in the form of an ideal σ/π bond mixing type, which provides flexible binding strength of oxygen intermediates, thus breaking the scaling relation of *OOH and*OH to be closer to optimal conditions. We believe that this work would set a new understanding for the design of high-efficiency RE-based materials towards the ORR.

更新日期：2023-10-10

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南