Description:
<jats:title>Abstract</jats:title><jats:p>Achieving high catalytic activity with a minimum amount of platinum (Pt) is crucial for accelerating the cathodic hydrogen evolution reaction (HER) in proton exchange membrane (PEM) water electrolysis, yet it remains a significant challenge. Herein, a directed dual‐charge pumping strategy to tune the <jats:italic>d</jats:italic>‐orbital electronic distribution of Pt nanoclusters for efficient HER catalysis is proposed. Theoretical analysis reveals that the ligand effect and electronic metal‐support interactions (EMSI) create an effective directional electron transfer channel for the <jats:italic>d</jats:italic>‐orbital electrons of Pt, which in turn optimizes the binding strength to H*, thereby significantly enhancing HER efficiency of the Pt site. Experimentally, this directed dual‐charge pumping strategy is validated by elaborating Sb‐doped SnO<jats:sub>2</jats:sub> (ATO) supported Fe‐doped PtSn heterostructure catalysts (Fe‐PtSn/ATO). The synthesized 3%Fe‐PtSn/ATO catalysts exhibit lower overpotential (requiring only 10.5 mV to reach a current density of 10 mA cm<jats:sup>−</jats:sup><jats:sup>2</jats:sup>), higher mass activity (28.6 times higher than commercial 20 wt.% Pt/C), and stability in the HER process in acidic media. This innovative strategy presents a promising pathway for the development of highly efficient HER catalysts with low Pt loading.</jats:p>