Mu Yajing, Zhang Dantong, Gao Tianyi, Wang Lina, Zhang Lei, Zou Xiaoxin, Zheng Weitao, Fan Jinchang, Cui Xiaoqiang
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Jilin University Changchun, Changchun, 130012, China.
College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar, 161006, China.
Angew Chem Int Ed Engl. 2025 Jul;64(27):e202505908. doi: 10.1002/anie.202505908. Epub 2025 May 10.
Developing efficient Ru-based catalysts is crucial in reducing reliance on costly Ir for the acidic oxygen evolution reaction (OER). However, these Ru-based catalysts face a fundamental stability challenge due to the highly reactive nature of lattice oxygen. In this work, we propose an effective strategy to stabilize lattice oxygen in 2D amorphous RuO through p-p orbital hybridization by incorporating dopants such as Al, Ga, and In. Notably, Ga doping exhibits remarkable acidic OER performance, leading to a 137 mV reduction in overpotential at 10 mA cm and a 125-fold improvement in stability compared to undoped RuO. This also surpasses the performances of most reported Ru-based catalysts. In contrast, doping with other elements from the same period, such as Mn, Co, or Cu, shows negligible improvements in catalytic performance. In situ electrochemical spectroscopic analysis, couples with theoretical calculations, reveals that the p-p orbital hybridization in the Ga-O coordination within Ga-RuO effectively reduces the reactivity of lattice oxygen, suppresses the overoxidation of Ru, and switches the reaction pathway from the lattice oxygen mechanism to the adsorbate evolution mechanism. This novel p-p orbital hybridization strategy holds great potential for the development of efficient and robust electrocatalysts for OER and beyond.
开发高效的钌基催化剂对于减少酸性析氧反应（OER）中对昂贵铱的依赖至关重要。然而，由于晶格氧的高反应活性，这些钌基催化剂面临着基本的稳定性挑战。在这项工作中，我们提出了一种有效的策略，通过引入铝、镓和铟等掺杂剂，通过p-p轨道杂化来稳定二维非晶RuO中的晶格氧。值得注意的是，镓掺杂表现出显著的酸性OER性能，在10 mA cm时过电位降低137 mV，与未掺杂的RuO相比，稳定性提高了125倍。这也超过了大多数报道的钌基催化剂的性能。相比之下，用同一周期的其他元素（如锰、钴或铜）掺杂，催化性能的改善可以忽略不计。原位电化学光谱分析与理论计算相结合，揭示了Ga-RuO中Ga-O配位内的p-p轨道杂化有效地降低了晶格氧的反应活性，抑制了Ru的过氧化，并将反应途径从晶格氧机制转变为吸附质析出机制。这种新颖的p-p轨道杂化策略在开发用于OER及其他领域的高效且稳定的电催化剂方面具有巨大潜力。
