Integration of Alloy Segregation and Surface CoO Hybridization in Carbon‐Encapsulated CoNiPt Alloy Catalyst for Superior Alkaline Hydrogen Evolution

Abstract Constructing an efficient alkaline hydrogen evolution reaction (HER) catalyst with low platinum (Pt) consumption is crucial for the cost reduction of energy devices, such as electrolyzers. Herein, nanoflower‐like carbon‐encapsulated CoNiPt alloy catalysts with composition segregation are designed by pyrolyzing morphology‐controlled and Pt‐proportion‐tuned metal–organic frameworks (MOFs). The optimized catalyst containing 15% CoNiPt NFs (15%: Pt mass percentage, NFs: nanoflowers) exhibits outstanding alkaline HER performance with a low overpotential of 25 mV at a current density of 10 mA cm −2 , far outperforming those of commercial Pt/C (47 mV) and the most advanced catalysts. Such superior activity originates from an integration of segregation alloy and Co‐O hybridization. The nanoflower‐like hierarchical structure guarantees the full exposure of segregation alloy sites. Density functional theory calculations suggest that the segregation alloy components not only promote water dissociation but also facilitate the hydrogen adsorption process, synergistically accelerating the kinetics of alkaline HER. In addition, the activity of alkaline HER is volcanically distributed with the surface oxygen content, mainly in the form of Co 3d O 2p hybridization, which is another reason for enhanced activity. This work provides feasible insights into the design of cost‐effective alkaline HER catalysts by coordinating kinetic reaction sites at segregation alloy and adjusting the appropriate oxygen content.