Recent efforts in anion-exchange membrane water electrolysis (AEMWE) focus on developing superior catalysts and membrane electrode assemblies to narrow the performance gaps compared with proton-exchange membrane water electrolysis (PEMWE). Here we present and characterize Ir-free AEMWE cells with NiX (X = Fe, Co or Mn) layered double hydroxide (LDH) catalyst-coated membranes with polarization characteristics and hydrogen productivities approaching those of acidic PEMWE cells, achieving >5 A cm⁻² at <2.2 V. Operando spectroscopy revealed a correlation between Ni⁴⁺ centres and redox-active O ligands with an O K-edge feature, attributed to µ₃-O ligands in the γ-LDH catalytic phase via density functional theory calculations. This computational–experimental study challenges the previously assumed correlation between spectral O K-edge features and oxygen evolution reaction performance in Ni-based LDH catalysts and provides insights from the molecular to the technological level demonstrating how redox-active Ni–O species and innovative catalyst-coated membrane preparation boost AEMWE performance to values rivalling state-of-the-art PEMWE cell technology.

阴离子交换膜水电解 （AEMWE） 的最新工作集中在开发卓越的催化剂和膜电极组件，以缩小与质子交换膜水电解 （PEMWE） 相比的性能差距。在这里，我们提出并表征了具有 NiX（X = Fe、Co 或 Mn）层状双氢氧化物 （LDH） 催化剂包被膜的无 Ir AEMWE 电池，其极化特性和氢生产率接近酸性 PEMWE 电池，在 <2.2 V 下达到 >5 A ^cm-2。原位光谱揭示了 Ni⁴⁺ 中心与具有 O K 边缘特征的氧化还原活性 O 配体之间的相关性， 通过密度泛函理论计算归因于 γ-LDH 催化相中的_{μ 3-O} 配体。这项计算-实验研究挑战了先前假设的 Ni 基 LDH 催化剂中光谱 O K-edge 特征与析氧反应性能之间的相关性，并提供了从分子到技术层面的见解，展示了氧化还原活性 Ni-O 物种和创新的催化剂包被膜制备如何将 AEMWE 性能提高到与最先进的 PEMWE 电池技术相媲美的值。