Zhang Luping, Chen Sijie, Du Tianheng, Zhao Xianzhe, Dong Anqi, Zhang Lifang, Li Tongfei, Li Linbo, Yan Chenglin, Qian Tao
School of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, China.
Chongqing Technology and Business University, Nan'an District, Chongqing 400067, China.
ACS Nano. 2024 Dec 17;18(50):34195-34206. doi: 10.1021/acsnano.4c11614. Epub 2024 Dec 3.
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 EuO immobilized within N-doped carbon nanofibers (Ru/EuO@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 EuO 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/EuO as the promising catalyst alternative for fast alkaline hydrogen electrooxidation. As a result, the Ru/EuO@N-CNFs reach an impressive kinetic current densities () value of 156.3 mA cm 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.
在推进阴离子交换膜燃料电池（AEMFCs）技术方面，寻求用于碱性氢氧化反应（HOR）的经济高效纳米材料势在必行。使用基于铂的电催化剂进行碱性HOR的努力受到其有限的本征活性和严重的CO中毒的极大困扰，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，通过d-p-f梯度轨道耦合策略，开发了负载在氮掺杂碳纳米纤维（Ru/EuO@N-CNFs）中的钌簇与氧化铕耦合的材料，以大幅提高对HOR的电催化性能。理论计算和原位操作光谱发现，氧化铕的引入通过构建Ru(3d)-O(2p)-Eu(4f)的梯度轨道耦合来优化Ru位点的电子结构，从而产生最佳的H中间体，提高OH的吸附能力，降低水形成的能垒，并促进CO氧化，使Ru/EuO成为快速碱性氢电氧化的有前途的催化剂替代品。结果，Ru/EuO@N-CNFs在50 mV时达到了令人印象深刻的156.3 mA cm的动力学电流密度（）值（比Pt/C高38.4倍），并且在连续运行35000 s以上具有良好的稳定性。这项以d-p-f梯度轨道耦合为特色的综合研究为高性能Ru基HOR及其他材料的战略开发提供了有价值的见解。
