Zhang Linjie, Hu Haihui, Sun Chen, Xiao Dongdong, Wang Hsiao-Tsu, Xiao Yi, Zhao Shuwen, Chen Kuan Hung, Lin Wei-Xuan, Shao Yu-Cheng, Wang Xiuyun, Pao Chih-Wen, Han Lili
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, China.
Nat Commun. 2024 Aug 21;15(1):7179. doi: 10.1038/s41467-024-51370-1.
The insufficient availability and activity of interfacial water remain a major challenge for alkaline hydrogen evolution reaction (HER). Here, we propose an "on-site disruption and near-site compensation" strategy to reform the interfacial water hydrogen bonding network via deliberate cation penetration and catalyst support engineering. This concept is validated using tip-like bimetallic RuNi nanoalloys planted on super-hydrophilic and high-curvature carbon nanocages (RuNi/NC). Theoretical simulations suggest that tip-induced localized concentration of hydrated K facilitates optimization of interfacial water dynamics and intermediate adsorption. In situ synchrotron X-ray spectroscopy endorses an H* spillover-bridged Volmer‒Tafel mechanism synergistically relayed between Ru and Ni. Consequently, RuNi/NC exhibits low overpotential of 12 mV and high durability of 1600 h at 10 mA cm for alkaline HER, and demonstrates high performance in both water electrolysis and chlor-alkali electrolysis. This strategy offers a microscopic perspective on catalyst design for manipulation of the local interfacial water structure toward enhanced HER kinetics.
界面水的可用性和活性不足仍然是碱性析氢反应（HER）面临的主要挑战。在此，我们提出一种“原位破坏和近位补偿”策略，通过有意的阳离子渗透和催化剂载体工程来改造界面水氢键网络。使用负载在超亲水和高曲率碳纳米笼（RuNi/NC）上的尖端状双金属RuNi纳米合金验证了这一概念。理论模拟表明，尖端诱导的水合钾局部浓度有助于优化界面水动力学和中间体吸附。原位同步辐射X射线光谱证实了一种在Ru和Ni之间协同传递的H*溢流桥连Volmer-Tafel机制。因此，RuNi/NC在碱性HER中表现出12 mV的低过电位和在10 mA cm下1600 h的高耐久性，并在水电解和氯碱电解中均表现出高性能。该策略为催化剂设计提供了一个微观视角，用于操纵局部界面水结构以增强HER动力学。
