Ke Jia, Zhu Wenxiang, Ji Yujin, Chen Jinxin, Li Chenchen, Wang Yue, Wang Qun, Huang Wei-Hsiang, Hu Zhiwei, Li Youyong, Shao Qi, Lu Jianmei
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu, 215123, P. R. China.
Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Jiangsu, 215123, P. R. China.
Angew Chem Int Ed Engl. 2025 Mar 24;64(13):e202422740. doi: 10.1002/anie.202422740. Epub 2025 Jan 14.
Anodic oxygen evolution reaction (OER) exhibits a sluggish four-electron transfer process, necessitating catalysts with exceptional catalytic activity to enhance its kinetic rate. Van der Waals layered oxides are ideal materials for catalyst design, yet its stability for acidic OER remains large obstacle. Doping provides a crucial way to improve the activity and stability simultaneously. However, doping in Van der Waals layered oxides remains a great challenge since it easily leads to lattice distortion or even the crystal structure damage. In this work, we successfully doping acid-resistant niobium (Nb) into Van der Waals layered edge-shared 1T phase iridium oxide (1 T-IrO) via alkali-assisted thermal method. 1 T-IrO with a 5 % Nb doping (NbIrO) only required an overpotential of 191 mV to achieve a current density of 10 mA cm in 0.5 M HSO, 56 mV lower than that of 1T-IrO. When applied in proton exchange membrane water electrolyzer, NbIrO show stable operation at a high current density of 1.2 A cm for over 50 days. Density functional theory calculation reveals that doping Nb changes the potential-determining step from the *OOH deprotonation process in 1 T-IrO to the *O-OH coupling process in NbIrO.
阳极析氧反应（OER）呈现出缓慢的四电子转移过程，因此需要具有卓越催化活性的催化剂来提高其动力学速率。范德华层状氧化物是催化剂设计的理想材料，但其在酸性OER中的稳定性仍然是一个巨大的障碍。掺杂是同时提高活性和稳定性的关键方法。然而，在范德华层状氧化物中进行掺杂仍然是一个巨大的挑战，因为它很容易导致晶格畸变甚至晶体结构破坏。在这项工作中，我们通过碱辅助热法成功地将耐酸铌（Nb）掺杂到范德华层状边缘共享的1T相氧化铱（1T-IrO）中。5% Nb掺杂的1T-IrO（NbIrO）在0.5 M HSO中仅需191 mV的过电位即可达到10 mA cm的电流密度，比1T-IrO低56 mV。当应用于质子交换膜水电解槽时，NbIrO在1.2 A cm的高电流密度下稳定运行超过50天。密度泛函理论计算表明，掺杂Nb将决速步骤从1T-IrO中的OOH去质子化过程转变为NbIrO中的O-OH偶联过程。
