Feng Qi, Zhu Penghui, Fan Donghua, Williams Mark C, Huang Gang, Zhao Jing
School of Applied Physics and Materials, Wuyi University, Jiangmen 529020, Guangdong, China; Jiangmen Advanced Battery Material Engineering and Technology Research Center, Jiangmen, Guangdong, 529020, China.
School of Applied Physics and Materials, Wuyi University, Jiangmen 529020, Guangdong, China.
J Colloid Interface Sci. 2025 Dec 15;700(Pt 2):138517. doi: 10.1016/j.jcis.2025.138517. Epub 2025 Jul 22.
Developing efficient and durable electrocatalysts for hydrogen evolution reaction (HER) is crucial for advancing sustainable energy technologies. Pyrochlore oxides show promise due to their structural versatility, but their application in HER is limited by weak hydrogen binding, poor conductivity, and insufficient active site exposure. Here, we demonstrate a controlled in-situ exsolution approach to create optimized RuIr/YO heterointerfaces from Ir-doped YRuO pyrochlore oxide. Through systematic tuning of reduction parameters, we achieve precise control over size and distribution of exsolved RuIr nanoparticles, forming intimate metal-oxide heterojunctions with enhanced charge transfer properties. The optimized YRIO-450-8H (YRuIrO reduced at 450 °C for 8 h) catalyst exhibits exceptional HER performance, requiring only 20 and 30 mV overpotential to deliver 10 mA cm in alkaline and acidic media, respectively, outperforming commercial Pt/C. Mechanistic investigations combining advanced characterizations and DFT calculations reveal that the remarkable activity stems from synergistic effects: (1) optimized hydrogen binding energy (-0.13 eV) at RuIr sites, (2) electronic structure modulation at the metal-oxide interface, and (3) abundant oxygen vacancies facilitating water dissociation. The catalyst maintains activity over 120 h in alkaline and 55 h in acidic conditions, providing fundamental insights into exsolution mechanisms and design principles for high-performance heterogeneous electrocatalysts.
开发用于析氢反应（HER）的高效耐用的电催化剂对于推进可持续能源技术至关重要。烧绿石氧化物因其结构的多样性而展现出潜力，但其在HER中的应用受到氢结合力弱、导电性差和活性位点暴露不足的限制。在此，我们展示了一种可控的原位析出方法，用于从铱掺杂的钇钌氧化物烧绿石中创建优化的RuIr/YO异质界面。通过系统调整还原参数，我们实现了对析出的RuIr纳米颗粒的尺寸和分布的精确控制，形成具有增强电荷转移特性的紧密金属 - 氧化物异质结。优化后的YRIO - 450 - 8H（在450°C下还原8小时的YRuIrO）催化剂表现出卓越的HER性能，在碱性和酸性介质中分别仅需20和30 mV的过电位即可达到10 mA cm，性能优于商业Pt/C。结合先进表征和DFT计算的机理研究表明，其卓越的活性源于协同效应：（1）RuIr位点处优化的氢结合能（-0.13 eV），（2）金属 - 氧化物界面处的电子结构调制，以及（3）丰富的氧空位促进水的解离。该催化剂在碱性条件下保持活性超过120小时，在酸性条件下保持55小时，为高性能多相电催化剂的析出机理和设计原则提供了基本见解。
