镧系元素调控的Ru-O共价性优化了酸性析氧电催化性能。
Lanthanide-regulating Ru-O covalency optimizes acidic oxygen evolution electrocatalysis.
作者信息
Li Lu, Zhang Gengwei, Zhou Chenhui, Lv Fan, Tan Yingjun, Han Ying, Luo Heng, Wang Dawei, Liu Youxing, Shang Changshuai, Zeng Lingyou, Huang Qizheng, Zeng Ruijin, Ye Na, Luo Mingchuan, Guo Shaojun
机构信息
School of Materials Science and Engineering, Peking University, Beijing, China.
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, Yunnan, China.
出版信息
Nat Commun. 2024 Jun 11;15(1):4974. doi: 10.1038/s41467-024-49281-2.
Precisely modulating the Ru-O covalency in RuO for enhanced stability in proton exchange membrane water electrolysis is highly desired. However, transition metals with d-valence electrons, which were doped into or alloyed with RuO, are inherently susceptible to the influence of coordination environment, making it challenging to modulate the Ru-O covalency in a precise and continuous manner. Here, we first deduce that the introduction of lanthanide with gradually changing electronic configurations can continuously modulate the Ru-O covalency owing to the shielding effect of 5s/5p orbitals. Theoretical calculations confirm that the durability of Ln-RuO following a volcanic trend as a function of Ru-O covalency. Among various Ln-RuO, Er-RuO is identified as the optimal catalyst and possesses a stability 35.5 times higher than that of RuO. Particularly, the Er-RuO-based device requires only 1.837 V to reach 3 A cm and shows a long-term stability at 500 mA cm for 100 h with a degradation rate of mere 37 μV h.
精确调节RuO中的Ru - O共价性以提高质子交换膜水电解中的稳定性是非常有必要的。然而，具有d价电子的过渡金属，无论是掺杂到RuO中还是与RuO合金化，本质上都易受配位环境的影响，这使得以精确且连续的方式调节Ru - O共价性具有挑战性。在此，我们首先推断，由于5s/5p轨道的屏蔽效应，引入具有逐渐变化电子构型的镧系元素可以连续调节Ru - O共价性。理论计算证实，Ln - RuO的耐久性呈现火山趋势，是Ru - O共价性的函数。在各种Ln - RuO中，Er - RuO被确定为最佳催化剂，其稳定性比RuO高35.5倍。特别地，基于Er - RuO的装置达到3 A cm²仅需1.837 V，并且在500 mA cm²下显示出100小时的长期稳定性，降解速率仅为37 μV h⁻¹。
Zotero 插件