Deng Liming, Hung Sung-Fu, Liu Shuyi, Zhao Sheng, Lin Zih-Yi, Zhang Chenchen, Zhang Ying, Wang Ai-Yin, Chen Han-Yi, Peng Jian, Ma Rongpeng, Jiao Lifang, Hu Feng, Li Linlin, Peng Shengjie
College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China.
Department of Applied Chemistry, National Yang Ming Chiao Tung University, Hsinchu 300, Taiwan.
J Am Chem Soc. 2024 Aug 21;146(33):23146-23157. doi: 10.1021/jacs.4c05070. Epub 2024 Aug 7.
The poor durability of Ru-based catalysts limits the practical application in proton exchange membrane water electrolysis (PEMWE). Here, we report that the asymmetric active units in RuMO (M = Sb, In, and Sn) binary solid solution oxides are constructed by introducing acid-resistant p-block metal sites, breaking the activity and stability limitations of RuO in acidic oxygen evolution reaction (OER). Constructing highly asymmetric Ru-O-Sb units with a strong electron delocalization effect significantly shortens the spatial distance between Ru and Sb sites, improving the bonding strength of the overall structure. The unique two-electron redox couples at Sb sites in asymmetric active units trigger additional chemical steps at different OER stages, facilitating continuous proton transfer. The optimized RuSbO solid solution requires a superlow overpotential of 160 mV at 10 mA cm and a record-breaking stability of 1100 h in an acidic electrolyte. Notably, the scale-prepared RuSbO achieves efficient PEMWE performance under industrial conditions. General mechanism analysis shows that the enhanced proton transport in the asymmetric Ru-O-M unit provides a new working pathway for acidic OER, breaking the scaling relationship without sacrificing stability.
钌基催化剂较差的耐久性限制了其在质子交换膜水电解（PEMWE）中的实际应用。在此，我们报道了通过引入耐酸性p区金属位点构建RuMO（M = Sb、In和Sn）二元固溶体氧化物中的不对称活性单元，打破了RuO在酸性析氧反应（OER）中的活性和稳定性限制。构建具有强电子离域效应的高度不对称Ru-O-Sb单元显著缩短了Ru和Sb位点之间的空间距离，提高了整体结构的结合强度。不对称活性单元中Sb位点独特的双电子氧化还原对在不同OER阶段触发额外的化学步骤，促进质子的持续转移。优化后的RuSbO固溶体在10 mA cm下需要160 mV的超低过电位，在酸性电解质中具有破纪录的1100 h稳定性。值得注意的是，规模化制备的RuSbO在工业条件下实现了高效的PEMWE性能。一般机理分析表明，不对称Ru-O-M单元中增强的质子传输为酸性OER提供了一条新的工作途径，打破了比例关系且不牺牲稳定性。
