Song Xuefen, Ayyob Muhammad, Su Panpan, Cui Jian, Li Wenxiu, Zhang Meng, Zhang Xuemin, Chen Zhongwei
Department of Chemistry, College of Sciences, Northeastern University, Shenyang, 110819, China.
Power Battery and Systems Research Center, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
Small. 2025 Aug;21(32):e2503357. doi: 10.1002/smll.202503357. Epub 2025 Jun 11.
The acidic electrolyte and highly oxidizing environment of proton exchange membrane water electrolysis (PEMWE) pose significant challenges to the stability of Ru-based anode catalysts and limit their practical applications. In this study, Co-doped RuO nanocrystals are synthesized using a one-step annealing method of Co-exchanged Ru-bpydc derivatives. The catalyst demonstrated excellent oxygen evolution reaction (OER) performance, achieving a low overpotential of 205 mV at 10 mA cm and superior stability, retaining activity for over 1000 h without degradation. Advanced characterization techniques revealed that cobalt doping increases oxygen vacancies and manipulates the reaction pathway by boosting the adsorbate evolution mechanism (AEM) and suppressing the participation of lattice oxygen in OER. Density functional theory (DFT) calculations further confirmed that the electron transfer between Ru and Co site via bridge O in the structure of Ru─O─Co optimized the adsorption energy of oxo-intermediates to promote AEM, thereby boosting stability. In addition, the Co─RuO catalyst exhibited good performance as an anode in a PEMWE, demonstrating stable operation for over 100 h at a current density of 100 mA cm. This work presents a viable approach to designing highly active and durable OER catalysts, making significant contributions to the advancement of PEMWE technology.
质子交换膜水电解（PEMWE）的酸性电解质和高氧化环境对钌基阳极催化剂的稳定性构成了重大挑战，并限制了它们的实际应用。在本研究中，通过钴交换的钌-联吡啶衍生物的一步退火法合成了钴掺杂的RuO纳米晶体。该催化剂表现出优异的析氧反应（OER）性能，在10 mA cm时过电位低至205 mV，并且具有出色的稳定性，在超过1000小时的时间内保持活性而不降解。先进的表征技术表明，钴掺杂增加了氧空位，并通过促进吸附质析出机制（AEM）和抑制晶格氧参与OER来控制反应途径。密度泛函理论（DFT）计算进一步证实，在Ru─O─Co结构中，Ru和Co位点之间通过桥连O的电子转移优化了氧代中间体的吸附能，从而促进了AEM，进而提高了稳定性。此外，Co─RuO催化剂在PEMWE中作为阳极表现出良好的性能，在100 mA cm的电流密度下稳定运行超过100小时。这项工作提出了一种设计高活性和耐用OER催化剂的可行方法，为PEMWE技术的进步做出了重大贡献。
