Shi Yue, Miao Hongfu, Gao Jianyang, Liu Feifei, Deng Ying, Li Hongdong, Chi Jingqi, Li Caixia, Liu Fusheng, Lai Jianping, Wang Lei
State Key Laboratory Base of Eco-Chemical Engineering, International Science and Technology Cooperation Base of Eco-chemical Engineering and Green Manufacturing, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR China.
State Key Laboratory Base of Eco-Chemical Engineering, College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR China.
J Colloid Interface Sci. 2025 Feb;679(Pt A):578-585. doi: 10.1016/j.jcis.2024.10.002. Epub 2024 Oct 5.
The sluggish kinetics and inherent instability over the Ru/RuO clusters are still enormous challenges in proton exchange membrane (PEM) water electrolyzer. Herein, we innovatively report synergistic modulation of dynamic electron modification and strong metal-support interaction (SMSI) to activate and stabilize bifunctional fluorine doped Ru/RuO clusters anchored on carbon nanotube (CNT), thus achieving efficient and stable acidic overall water splitting. Theoretical and experimental studies found that surface metal-fluorine modification layer could dynamically regulate the interfacial electronic environment to stabilize and activate multiple active Ru species; and the SMSI between Ru/RuO cluster and CNT maintains stable electronic environment for dynamic electron modification and avoids migrating or shedding of active species in acidic environment. Therefore, the PEM electrolyzer assembled with optimal F-Ru/RuO@CNT can operate stably for 100 h at a high current density of 100 mA cm, which is the first time that bifunctional Ru-based nanocatalysts applied to PEM device at a high current density.
钌/氧化钌团簇缓慢的动力学过程和固有的不稳定性仍然是质子交换膜（PEM）水电解槽面临的巨大挑战。在此，我们创新性地报道了通过动态电子修饰和强金属-载体相互作用（SMSI）的协同调制，来激活和稳定锚定在碳纳米管（CNT）上的双功能氟掺杂钌/氧化钌团簇，从而实现高效稳定的酸性全水分解。理论和实验研究发现，表面金属-氟修饰层可以动态调节界面电子环境，以稳定和激活多种活性钌物种；并且钌/氧化钌团簇与碳纳米管之间的SMSI为动态电子修饰维持稳定的电子环境，并避免活性物种在酸性环境中迁移或脱落。因此，采用最优的F-Ru/RuO@CNT组装的PEM电解槽能够在100 mA cm的高电流密度下稳定运行100小时，这是双功能钌基纳米催化剂首次在高电流密度下应用于PEM装置。
