Metallic Ru─Ru Interaction in Ruthenium Oxide Enabling Durable Proton Exchange Membrane Water Electrolysis

• Published in: Advanced materials (Weinheim) 2024-07, Vol.36 (30), p.e2404213-n/a
• Main Authors: Zhao, Guoqiang, Guo, Wei, Shan, Minmin, Fang, Yanyan, Wang, Gongming, Gao, Mingxia, Liu, Yongfeng, Pan, Hongge, Sun, Wenping
• Format: Article
• Language: English
• Subjects: Dissolution; Durability; electrocatalysis; Electrocatalysts; Electrochemical corrosion; Electrolysis; Membranes; oxygen evolution reaction; Oxygen evolution reactions; proton exchange membrane water electrolysis; Protons; Robustness; ruthenium dissolution; Ruthenium oxide; Stability
• ISSN: 0935-9648; 1521-4095; 1521-4095
• DOI: 10.1002/adma.202404213

Developing efficient and robust electrocatalysts toward the oxygen evolution reaction (OER) is critical for proton exchange membrane water electrolysis (PEMWE). RuO2 possesses intrinsically high OER activity, but the concurrent electrochemical dissolution leads to rapid deactivation. Here a unique RuO2 catalyst containing metallic Ru─Ru interactions (m‐RuO2) is reported, which maintains stability in practical PEMWE for 100 h at 60 °C and 1 A cm−2. Experimental and theoretical investigations suggest that the presence of Ru─Ru interactions significantly increases the energy barrier for the formation of RuO2(OH)2, which is a key intermediate for Ru dissolution, and hence substantially mitigates the electrochemical corrosion of m‐RuO2. Meanwhile, the Ru4d band center downshifts, accordingly, ensuring the high OER activity, and the participation of lattice oxygen in the OER is also suppressed at the Ru─Ru sites, further contributing to the enhanced durability. Interestingly, such enhanced stability is also dependent on the size of metallic Ru─Ru cluster, where the energy barrier is further increased for Ru3, but is decreased for Ru5. These results highlight the significance of local coordination structure modulation on the electrochemical stability of RuO2 and open a feasible avenue toward the development of robust OER electrocatalysts for high‐performance PEMWE. A unique RuO2 catalyst containing metallic Ru─Ru interactions (m‐RuO2) is developed, which demonstrates great stability in proton exchange membrane water electrolysis. The under‐coordinate Ru species are stabilized and the energy barrier for Ru dissolution is increased due to the presence of Ru─Ru interactions. These results highlight the significance of local coordination structure modulation in developing robust electrocatalysts.