Zhou Chenhui, Li Lu, Dong Zhaoqi, Lv Fan, Guo Hongyu, Wang Kai, Li Menggang, Qian Zhengyi, Ye Na, Lin Zheng, Luo Mingchuan, Guo Shaojun
School of Materials Science and Engineering, Peking University, Beijing, China.
Nat Commun. 2024 Nov 12;15(1):9774. doi: 10.1038/s41467-024-53905-y.
Ruthenium (Ru) is widely recognized as a low-cost alternative to iridium as anode electrocatalyst in proton-exchange membrane water electrolyzers (PEMWE). However, the reported Ru-based catalysts usually only operate within tens of hours in PEMWE because of their intrinsically high reactivity of lattice oxygen that leads to irrepressible Ru leaching and structural collapse. Herein, we report a design concept by employing large-sized and acid-resistant lattice lead (Pb) as a second element to induce a pinning effect for effectively narrowing the moving channels of oxygen atoms, thereby lowering the reactivity of lattice oxygen in Ru oxides. The Pb-RuO catalyst presents a low overpotential of 188 ± 2 mV at 10 mA cm and can sustain for over 1100 h in an acid medium with a negligible degradation rate of 19 μV h. Particularly, the Pb-RuO-based PEMWE can operate for more than 250 h at 500 mA cm with a low degradation rate of only 17 μV h. Experimental and theoretical calculation results reveal that Ru-O covalency is reduced due to the unique 6s-2p-4d orbital hybridization, which increases the loss energy of lattice oxygen and suppresses the over-oxidation of Ru for improved long-term stability in PEMWE.
钌(Ru)作为质子交换膜水电解槽(PEMWE)中阳极电催化剂,被广泛认为是铱的低成本替代品。然而,由于其晶格氧固有的高反应活性会导致无法抑制的Ru浸出和结构坍塌,报道的Ru基催化剂在PEMWE中通常只能运行数十小时。在此,我们报告一种设计理念,即采用大尺寸且耐酸的晶格铅(Pb)作为第二元素,以诱导钉扎效应,有效缩小氧原子的移动通道,从而降低Ru氧化物中晶格氧的反应活性。Pb-RuO催化剂在10 mA cm时呈现出188±2 mV的低过电位,在酸性介质中可持续运行超过1100小时,降解速率可忽略不计,为19 μV h。特别地,基于Pb-RuO的PEMWE在500 mA cm下可运行超过250小时,降解速率仅为17 μV h。实验和理论计算结果表明,由于独特的6s-2p-4d轨道杂化,Ru-O共价性降低,这增加了晶格氧的损失能量,并抑制了Ru的过度氧化,从而提高了PEMWE中的长期稳定性。