Zhang Xiuxiu, Zhang Yuhao, Protsenko Bogdan O, Soldatov Mikhail A, Zhang Jing, Yang Chenyu, Bo Shuowen, Wang Huijuan, Chen Xin, Wang Chao, Cheng Weiren, Liu Qinghua
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui, PR China.
School of Chemistry and Material Sciences, University of Science and Technology of China, Hefei, Anhui, PR China.
Nat Commun. 2025 Jul 28;16(1):6921. doi: 10.1038/s41467-025-62258-z.
The development of non-iridium-based oxygen evolution reaction (OER) catalysts is crucial for proton exchange membrane water electrolysis (PEMWE), but hydrogen production remains a great challenge because of sluggish OER kinetics and severe catalyst dissolution. Here, we present a 4f-induced covalent polarity modulation strategy for the construction of 4f-orbital-modified RuO (4f-RuO) nanocatalysts with tunable Ru-O polarity. We find that the OER activity of 4f-RuO shows a volcano shape as a function of the polarity of Ru-O bond. Consequently, the best 4f-Nd-RuO catalyst possesses an ultra-low overpotential of 214 mV at 10 mA cm and robust electrochemical stability in 0.1 M HClO. Theoretical calculations coupled with in situ synchrotron infrared and X-ray absorption spectroscopy analyses reveal that the modulation of Ru-O polarity in RuO by the valence f-p-d gradient orbital coupling can modify the adsorption energy of the reaction intermediates and suppress the participation of lattice oxygen to avoid over-oxidation of Ru, which can thus serve as an effective descriptor for fine tuning the activity and durability of acidic OER nanocatalysts.
开发非铱基析氧反应（OER）催化剂对于质子交换膜水电解（PEMWE）至关重要，但由于OER动力学缓慢和催化剂严重溶解，制氢仍然是一个巨大的挑战。在此，我们提出一种4f诱导的共价极性调制策略，用于构建具有可调Ru-O极性的4f轨道修饰的RuO（4f-RuO）纳米催化剂。我们发现，4f-RuO的OER活性随Ru-O键的极性呈火山形状变化。因此，最佳的4f-Nd-RuO催化剂在10 mA cm时具有214 mV的超低过电位，并且在0.1 M HClO中具有稳健的电化学稳定性。理论计算结合原位同步辐射红外和X射线吸收光谱分析表明，通过价态f-p-d梯度轨道耦合对RuO中Ru-O极性的调制可以改变反应中间体的吸附能，并抑制晶格氧的参与以避免Ru的过度氧化，这因此可以作为微调酸性OER纳米催化剂活性和耐久性的有效描述符。
