Eskandari Parisa, Zhou Shujie, Yuwono Jodie, Gunawan Denny, Webster Richard F, Ma Zhipeng, Xu Hanyu, Amal Rose, Lu Xunyu
School of Chemical Engineering, University of New South Wales (UNSW) Sydney, Kensington, NSW, 2052, Australia.
School of Chemical Engineering, University of Adelaide, Adelaide, South Australia, 5005, Australia.
Adv Mater. 2025 Aug;37(34):e2419360. doi: 10.1002/adma.202419360. Epub 2025 Mar 20.
Precisely optimizing the electronic metal support interaction (EMSI) of the electrocatalysts and tuning the electronic structures of active sites are crucial for accelerating water adsorption and dissociation kinetics in alkaline hydrogen evolution reaction (HER). Herein, an effective strategy is applied to modify the electronic structure of Ru nanoparticles (Ru) by incorporating Ru single atoms (Ru) and Ru and Cr atomic pairs (RuCr) onto a nitrogen-doped carbon (N-C) support through optimized EMSI. The resulting catalyst, Ru-RuCr-N-C, shows exceptional performance for alkaline HER, achieving a six times higher turnover frequency (TOF) of 13.15 s⁻¹ at an overpotential of 100 mV, compared to that of commercial Pt/C (2.07 s⁻¹). Additionally, the catalyst operates at a lower overpotential at a current density of 10 mA·cm⁻ (η = 31 mV), outperforming commercial Pt/C (η = 34 mV). Experimental results confirm that the RuCr modified Ru are the main active sites for the alkaline HER, facilitating the rate-determining steps of water adsorption and dissociation. Moreover, the Ru-Cr interaction also plays a vital role in modulating hydrogen desorption. This study presents a synergistic approach by rationally combining single atoms, atomic pairs, and nanoparticles with optimized EMSI effects to advance the development of efficient electrocatalysts for alkaline HER.
精确优化电催化剂的电子-金属载体相互作用（EMSI）并调节活性位点的电子结构对于加速碱性析氢反应（HER）中的水吸附和解离动力学至关重要。在此，通过优化的EMSI将Ru单原子（Ru）以及Ru和Cr原子对（RuCr）掺入氮掺杂碳（N-C）载体上，应用一种有效策略来修饰Ru纳米颗粒（Ru）的电子结构。所得催化剂Ru-RuCr-N-C在碱性HER中表现出优异性能，在100 mV过电位下实现了13.15 s⁻¹的周转频率（TOF），是商业Pt/C（2.07 s⁻¹）的六倍。此外，该催化剂在10 mA·cm⁻²电流密度下以更低的过电位运行（η = 31 mV），优于商业Pt/C（η = 34 mV）。实验结果证实，RuCr修饰的Ru是碱性HER的主要活性位点，促进了水吸附和解离的速率决定步骤。此外，Ru-Cr相互作用在调节氢脱附方面也起着至关重要的作用。本研究提出了一种协同方法，通过合理组合单原子、原子对和纳米颗粒并具有优化的EMSI效应，以推动用于碱性HER的高效电催化剂的发展。
