Xu Jun, Kao Chun-Chuan, Shen Haifeng, Liu Hao, Zheng Yao, Qiao Shi-Zhang
School of Chemical Engineering, The University of Adelaide, Adelaide, SA 5005, Australia.
Angew Chem Int Ed Engl. 2025 Feb 24;64(9):e202420615. doi: 10.1002/anie.202420615. Epub 2024 Dec 4.
Currently, direct electrolysis of seawater for green hydrogen production is primarily focused on neutral and alkaline systems. However, the precipitation of calcium and magnesium ions restricts the advancement of this technology. An acidic system can effectively address this issue. Given that Ru/Ir-based catalysts with high oxygen evolution reaction (OER) activity also exhibit high chlorine evolution reaction (CER) activity, acid seawater splitting requires anodes with higher selectivity and stability compared to the other two systems. In this study, we propose a non-precious RuMnO as the active anode for direct acid seawater electrolysis, which exhibits a high OER selectivity and remarkable stability for more than 1200 hours. Different from the Cl-free system, *Cl occupied on Ru sites could shift the OER active center to Mn on RuMnO, which prevents the lattice oxygen consumed on Ru and hinders the metal site dissolution. As the CER-insensitive catalytic center, Mn activated by the introduction of Ru can adsorb a substantial amount of *OH, creating an OER-favored local environment that inhibits CER. We introduce Cl-assisted transfer of OER active sites to CER-insensitive Mn as a fundamental strategy for achieving highly selective and durable oxygen evolution in acidic seawater.
目前,用于绿色制氢的海水直接电解主要集中在中性和碱性体系。然而,钙和镁离子的沉淀限制了该技术的发展。酸性体系可以有效解决这个问题。鉴于具有高析氧反应(OER)活性的钌/铱基催化剂也表现出高析氯反应(CER)活性,与其他两个体系相比,酸性海水分解需要具有更高选择性和稳定性的阳极。在本研究中,我们提出了一种非贵金属RuMnO作为直接酸性海水电解的活性阳极,它表现出高OER选择性和超过1200小时的显著稳定性。与无氯体系不同,Ru位点上占据的Cl可以将OER活性中心转移到RuMnO上的Mn,这防止了Ru上的晶格氧消耗并阻碍了金属位点溶解。作为对CER不敏感的催化中心,通过引入Ru活化的Mn可以吸附大量的*OH,创造一个有利于OER的局部环境,抑制CER。我们引入Cl辅助的OER活性位点向对CER不敏感的Mn转移,作为在酸性海水中实现高选择性和持久析氧的基本策略。