Interfacial Water Reorganization via Polyethyleneimine‐Functionalization for Enhanced Alkaline Hydrogen Evolution on Single‐Atom Platinum Anchored on Reduced Graphene Oxide

ABSTRACT Microstructure and interface engineering of electrocatalysts are vital for enhancing alkaline hydrogen evolution (HER) by addressing kinetic barriers at the electrode‐electrolyte interface. Here, we introduce a dual‐function catalyst with single‐atom Pt active sites supported on a polyethyleneimine‐functionalized reduced graphene oxide scaffold, RGO‐PEI/Pt 1 , for alkaline HER. Electrochemical analysis reveals that RGO‐PEI/Pt 1 exhibited a superior HER activity with a very low overpotential of 32 mV at j = 10 mA cm −2 , a Tafel slope of 51 mV dec −1 , and a reduced charge transfer resistance of 2.5 Ω. Advanced characterization analysis confirms PEI's active role in forming hydrogen bonds with interfacial water. Density functional theory (DFT) calculation illustrated that primary amines on the PEI backbone anchor Pt atoms, while secondary amines facilitate proton delivery by maintaining a connected hydrogen‐bond network at the interface. Additionally, the semi‐linear configuration of Pt single atoms enables sequential hydrogen adsorption of up to four H + ions per Pt atom, ensuring optimal surface coverage and accelerating the HER. This work establishes a cooperative design approach that enables atomic‐scale stabilization and interfacial hydration, leading to high HER activity with low Pt loading. The model not only supports efficient alkaline hydrogen production but also provides a template for designing future electrocatalysts.