High-entropy intermetallics for electrocatalysis: Harnessing enthalpy–entropy trade-off

Entropy-effects engineering represents a critical paradigm shift in nanomaterial design. High-entropy intermetallics (HEIs) integrate the vast compositional space of high-entropy alloys with the structural precision of intermetallic phases, confining chemical complexity within well-defined periodic structures. However, the inherent trade-off between entropy-driven disordering and enthalpy-driven ordering confines these materials to a narrow metastable window, posing significant challenges for their targeted synthesis. Focusing on the intricate correlations between structure, composition, and catalytic performance, this review summarizes recent progress in the synthesis of HEIs. By dissecting the enthalpy–entropy trade-off that governs the degree of ordering, the role of negative mixing enthalpy in determining phase evolution is elucidated, establishing design principles for tailoring the structure of HEIs. Furthermore, the integration of advanced characterization techniques with electrochemical analysis is highlighted as a cornerstone for establishing a research paradigm built on multiple characterizations. Finally, we discuss challenges and perspectives on quantifying the entropy–enthalpy trade-off, elemental design, controllable synthesis, and multi-path electrochemistry of HEIs, offering new pathways for widespread catalytic application.