Yang Ming, Guan Xin, Shi Zhaoping, Wu Hongxiang, Cheng Yuqing, Wang Ziang, Liu Wei, Xiao Fei, Shao Minhua, Xiao Meiling, Liu Changpeng, Xing Wei
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin, 130022, China.
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, Anhui, 230026, China.
Small. 2025 Jan 16:e2411117. doi: 10.1002/smll.202411117.
The scarcity of cost-effective and durable iridium-free anode electrocatalysts for the oxygen evolution reaction (OER) poses a significant challenge to the widespread application of the proton exchange membrane water electrolyzer (PEMWE). To address the electrochemical oxidation and dissolution issues of Ru-based electrocatalysts, an electron-donating modification strategy is developed to stabilize WRuO under harsh oxidative conditions. The optimized catalyst with a low Zirconium doping (Zr, 1 wt.%) enhances durability noticeably, with a 77% reduction in degradation rate in the durability test of 10 mA cm in 0.5 m HSO. When integrated into a homemade PEMWE device, the Zr-doped catalyst achieves excellent long-term stability, lasting up to 650 h at 100 mA cm⁻. Additionally, the electronic modulation from the Zr modification leads to superior activity with a low overpotential of 208 mV at 10 mA cm. Theoretical calculation results further reveal that electron-donating Zr modification effectively suppresses Ru overoxidation and lattice oxygen participation, maintaining a robust structure during acidic OER. This modification also promotes deprotonation through stronger Brønsted acid sites, significantly improving both long-term stability and activity.
用于析氧反应（OER）的具有成本效益且耐用的无铱阳极电催化剂的稀缺，对质子交换膜水电解槽（PEMWE）的广泛应用构成了重大挑战。为了解决基于钌的电催化剂的电化学氧化和溶解问题，开发了一种给电子修饰策略，以在苛刻的氧化条件下稳定WRuO。具有低锆掺杂（Zr，1 wt.%）的优化催化剂显著提高了耐久性，在0.5 m HSO中10 mA cm的耐久性测试中降解率降低了77%。当集成到自制的PEMWE装置中时，Zr掺杂催化剂实现了优异的长期稳定性，在100 mA cm⁻下可持续长达650 h。此外，Zr修饰引起的电子调制导致了优异的活性，在10 mA cm时过电位低至208 mV。理论计算结果进一步表明，给电子的Zr修饰有效地抑制了Ru的过度氧化和晶格氧的参与，在酸性OER过程中保持了稳定的结构。这种修饰还通过更强的布朗斯特酸位点促进去质子化，显著提高了长期稳定性和活性。
