<br>通过 Ru-O-Eu 桥以高效和 CO 耐受性加速碱性氢氧化的 Volmer 步骤,ACS Nano

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通过 Ru-O-Eu 桥以高效和 CO 耐受性加速碱性氢氧化的 Volmer 步骤
ACS Nano ( IF 15.8 ) Pub Date : 2024-12-03 , DOI: 10.1021/acsnano.4c11614
Luping Zhang ₁ , Sijie Chen ₁ , Tianheng Du ₁ , Xianzhe Zhao ₁ , Anqi Dong ₁ , Lifang Zhang ₁ , Tongfei Li ₁ , Linbo Li _{2,

3} , Chenglin Yan _{4,

5} , Tao Qian ₁

Affiliation

为碱性氢氧化反应（HOR）寻找经济高效的纳米材料对于推进阴离子交换膜燃料电池（AEMFC）的技术至关重要。使用 Pt 基电催化剂进行碱性 HOR 的努力受到其有限的本征活性和严重的 CO 中毒的严重困扰，这源于同时优化对不同氢相关吸附物的表面吸附的困难。在此，Ru 团簇与固定在 N 掺杂碳纳米纤维（Ru/Eu₂O₃@N-CNF）中的 Eu₂O₃ 偶联，通过 d-p-f 梯度轨道耦合策略发展为大幅提升的 HOR 电催化。理论计算和原位光谱发现，Eu₂O₃ 的诱导通过构建 Ru（3d）-O（2p）-Eu（4f）的梯度轨道耦合优化了 Ru 位电子结构，从而产生了最佳的 H 中间体，提高了 OH 的吸附能力，降低了水形成的能垒，促进了 CO 氧化，赋予 Ru/Eu₂O₃ 作为快速碱性氢电氧化的有前途的催化剂替代品。因此，Ru/Eu₂O₃@N-CNF 在 50 mV 时达到了令人印象深刻的 156.3 mA cm^–2 动电流密度（j_k）值（比 Pt/C 高 38.4 倍），并且在 35000 s 的连续运行中具有不错的稳定性。这项以 d-p-f 梯度轨道耦合为特色的全面研究为 HOR 及其他高性能 Ru 基材料的战略发展提供了宝贵的见解。

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Expediting the Volmer Step of Alkaline Hydrogen Oxidation with High-Efficiency and CO-Tolerance by Ru–O–Eu Bridge

The quest for economical and highly efficient nanomaterials for the alkaline hydrogen oxidation reaction (HOR) is imperative in advancing the technology of anion exchange membrane fuel cells (AEMFCs). Efforts using Pt-based electrocatalysts for alkaline HOR are greatly plagued by their finitely intrinsic activities and significant CO poisoning, stemming from the difficulty of simultaneously optimizing surface adsorption toward different hydrogen-related adsorbates. Herein, Ru clusters coupled with Eu₂O₃ immobilized within N-doped carbon nanofibers (Ru/Eu₂O₃@N-CNFs) are developed toward drastically boosted electrocatalysis for HOR via a d-p-f gradient orbital coupling strategy. Theoretical calculations and in situ operando spectroscopy discover that the induction of Eu₂O₃ optimizes the Ru site electronic structure via constructing the gradient orbital coupling of Ru(3d)-O(2p)-Eu(4f), leading to optimal H intermediates, improved adsorption ability of OH and reduced energy barrier of water formation, and promoted CO oxidation, endowing the Ru/Eu₂O₃ as the promising catalyst alternative for fast alkaline hydrogen electrooxidation. As a result, the Ru/Eu₂O₃@N-CNFs reach an impressive kinetic current densities (j_k) value of 156.3 mA cm^–2 at 50 mV (38.4 times higher than Pt/C), and decent stability over 35000 s continuous operation. This comprehensive investigation featuring d-p-f gradient orbital coupling provides valuable insights for the strategic development of high-performance Ru-based materials for HOR and beyond.

更新日期：2024-12-03

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