Lanthanide–O–Ru on RuO2 Mediates the Binding Behavior of OH, Enabling Efficient and Stable Water Oxidation in Acidic Solution

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-06-17 DOI:10.1021/acscatal.5c02124

Xuefen Song, Haoren Zheng, Jie Zhang, Xuejiang Zhang, Jian Cui, Muhammad Ayyob, Chuangwei Liu, Panpan Su, Zhongwei Chen

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Abstract

The development of Ru-based electrocatalysts with superior activity and stability for proton exchange membrane water oxidation remains a significant challenge. A key strategy is the precise engineering of the lanthanide–O–Ru structure to tailor surface species and continuously modulate Ru–O covalency, thereby optimizing the adsorption energy of intermediate species for enhanced catalytic performance. In this study, density functional theory (DFT) calculations predict that incorporating the late lanthanides (Tm–O–Ru) into the RuO₂ structure significantly enhances the density of states near the Fermi level to a greater extent than the middle lanthanide (Gd–O–Ru). This leads to a lower energy barrier for *OOH as the rate-determining step of the oxygen evolution reaction (OER). Additionally, the strength of *OH adsorption follows the Tm–O–Ru > Gd–O–Ru > RuO₂ trend. Experimental results confirm the theoretical predictions: Tm–O–Ru structure enhances the Ru–O covalency, tunes the electronic structure of Ru, and optimizes *OH adsorption. These modifications result in good OER performance with an overpotential of 201 mV and robust stability over 1000 h at 10 mA cm^–2. Furthermore, a Tm–RuO₂-based PEMWE device stably operates at 100 mA cm^–2 for 200 h with a low degradation rate of 0.195 mV h^–1, outperforming most Ru-based catalysts reported in the literature.

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镧系- o - ru在RuO2上介导OH的结合行为，实现酸性溶液中高效稳定的水氧化

开发具有优良活性和稳定性的钌基质子交换膜水氧化电催化剂仍然是一个重大的挑战。一个关键的策略是对镧系- o - ru结构进行精确的工程设计，以定制表面物种并连续调节Ru-O共价，从而优化中间物种的吸附能以提高催化性能。在本研究中，密度泛函理论（DFT）计算预测，将晚期镧系元素（Tm-O-Ru）加入到RuO2结构中，显著提高了费米能级附近态的密度，其程度大于中期镧系元素（Gd-O-Ru）。这导致*OOH作为析氧反应（OER）的速率决定步骤具有较低的能垒。此外，*OH吸附强度遵循Tm-O-Ru >；Gd-O-Ru祝辞RuO2趋势。实验结果证实了理论预测：Tm-O-Ru结构增强了Ru - o共价，调整了Ru的电子结构，优化了*OH吸附。这些改进导致了良好的OER性能，过电位为201 mV，在10 mA cm-2下超过1000小时的稳定性能。此外，基于tm - ruo2的PEMWE装置在100 mA cm-2下稳定工作200小时，降解率为0.195 mV h - 1，优于文献中报道的大多数基于ru的催化剂。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.