The Sabatier principle is widely explored in heterogeneous catalysis, graphically depicted in volcano plots. The most desirable activity is located at the peak of the volcano, and further advances in activity past this optimum are possible by designing a catalyst that circumvents the limitation entailed by the Sabatier principle. Herein, by density functional theory calculations, we discovered an unusual Sabatier principle on high entropy alloy (HEA) surface, distinguishing the “just right” (ΔG_H* = 0 eV) in the Sabatier principle of hydrogen evolution reaction (HER). A new descriptor was proposed to design HEA catalysts for HER. As a proof-of-concept, the synthesized PtFeCoNiCu HEA catalyst endows a high catalytic performance for HER with an overpotential of 10.8 mV at −10 mA cm⁻² and 4.6 times higher intrinsic activity over the state-of-the-art Pt/C. Moreover, the unusual Sabatier principle on HEA catalysts can be extended to other catalytic reactions.

萨巴蒂尔原理在多相催化领域得到了广泛的探索，并在火山图中进行了图形化描述。最理想的活性位于火山的顶峰，通过设计一种规避萨巴蒂尔原理所带来的限制的催化剂，可以进一步提高超过该最佳活性的活性。在此，通过密度泛函理论计算，我们在高熵合金（HEA）表面发现了一个不寻常的萨巴蒂尔原理，区分了析氢反应（HER）萨巴蒂尔原理中的“恰到好处”（Δ G _H* = 0 eV）。提出了一种新的描述符来设计 HER 的 HEA 催化剂。作为概念验证，合成的 PtFeCoNiCu HEA 催化剂赋予了 HER 较高的催化性能，在 -10 mA cm ^-2下的过电势为 10.8 mV，内在活性比最先进的 Pt/ 高 4.6 倍。 C。此外，HEA 催化剂上不寻常的 Sabatier 原理可以扩展到其他催化反应。