High-entropy materials (HEMs) have garnered tremendous attention for electrocatalytic water oxidation because of their extraordinary properties. Nevertheless, scant attention has been directed toward comprehending the origin of their excellent activity and intricate atomic arrangements. Herein, we demonstrate the synthesis of high-entropy metal selenides (HEMSs) using a rapid joule-heating method, effectively circumventing the immiscibility challenges inherent in combining multiple metal elements. This achievement is collectively verified by a convergence of diverse analytical techniques encompassing quasi in situ X-ray absorption spectroscopy and operando attenuated total reflectance infrared spectroscopy. The HEMS exhibits a low overpotential of 222 mV at 10 mA cm⁻² and extraordinary durability with negligible degradation over a 1,000 h durability test at 10 mA cm⁻² and 500 h at 100 mA cm⁻². Further, our theoretical investigations establish the pronounced mechanism of asymmetric Cu-Co-Ni active units in HEMS by manipulating the interaction of oxygen-containing intermediates, which leads to enhanced OER activity and durability.

高熵材料（HEM）因其非凡的性能而在电催化水氧化方面引起了极大的关注。然而，人们很少关注理解它们出色的活性和复杂的原子排列的起源。在此，我们展示了使用快速焦耳加热方法合成高熵金属硒化物（HEMS），有效地规避了组合多种金属元素所固有的不混溶性挑战。这一成就通过包括准原位 X 射线吸收光谱和操作衰减全反射红外光谱在内的多种分析技术的融合得到了共同验证。 HEMS 在 10 mA cm ⁻² 下表现出 222 mV 的低过电势，并且具有非凡的耐用性，在 10 mA cm ⁻² 下 1,000 小时耐久性测试和 100 mA cm 下 500 小时的耐用性测试中，退化可以忽略不计。 ⁻² 。此外，我们的理论研究通过操纵含氧中间体的相互作用，建立了 HEMS 中不对称 Cu-Co-Ni 活性单元的显着机制，从而增强了 OER 活性和耐久性。