High investment costs and a dependence on noble metal catalysts currently obstruct the large‐scale implementation of proton exchange membrane water electrolyzers (PEMWEs) for converting fluctuating green electricity into chemical energy via water splitting. In this context, this work presents a high‐performing and stable non‐noble metal catalyst for the hydrogen evolution reaction (HER), consisting of [Mo₃S₁₃]²⁻ clusters supported on nitrogen doped carbon nanotubes (NCNTs). Strikingly, a significant electrochemically induced activation of the Mo₃S₁₃‐NCNT catalyst at high current densities is observed in full cell configuration, enabling a remarkable current density of 4 A cm⁻² at a cell voltage of 2.36 V. To the authors’ knowledge, this is the highest reported value to date for a PEMWE full cell using a non‐noble metal HER catalyst. Furthermore, only a minor degradation of 83 µV h⁻¹ is observed during a stability test of 100 h constant current at 1 A cm⁻², with a nearly unchanged polarization behavior after the current hold. Catalyst stability and activity are additionally analyzed via online dissolution measurements. X‐ray photoelectron spectroscopy examination of the catalyst before and after electrochemical application reveals a correlation between the electrochemical activation occurring via electrodissolution with changes in the molecular structure of the Mo₃S₁₃‐NCNT catalyst.

中文翻译：

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基于非贵金属阴极催化剂：[Mo3 S13] 2-团簇固定在N掺杂碳纳米管上的鲁棒PEM水电解槽的制造。

目前，高昂的投资成本和对贵金属催化剂的依赖阻碍了质子交换膜水电解器（PEMWE）的大规模实施，该电解器通过水分解将波动的绿色电能转化为化学能。在此背景下，这项工作提出了一种用于氢释放反应（HER）的高性能且稳定的非贵金属催化剂，该催化剂由负载在氮掺杂碳纳米管（NCNT）上的[Mo ₃ S ₁₃ ] ^2-簇组成。引人注目的是，在全电池配置下，在高电流密度下观察到了Mo ₃ S ₁₃ ‐NCNT催化剂的明显电化学诱导活化，从而实现了4 A cm ^-2的显着电流密度在电池电压为2.36 V的情况下。据作者所知，这是迄今为止使用非贵金属HER催化剂的PEMWE全电池的最高报道值。此外，在1 A cm ^-2的100 h恒定电流的稳定性测试中，仅观察到83 µV h ^-1的较小劣化，在保持电流后，极化行为几乎不变。催化剂的稳定性和活性还通过在线溶解度分析进行了分析。电化学应用前后的X射线光电子能谱检查表明，通过电溶解发生的电化学活化与Mo ₃ S ₁₃ -NCNT催化剂的分子结构变化之间具有相关性。