Engineering Relative Spatial Structure of Dual Atomic Sites with Asymmetric Coordination for High‐Performance Hydrogen Evolution Activity

Dual‐atom catalysts (DACs), which extend single‐atom catalysts (SACs) with their dual‐site properties, are promising for mediating complex reaction intermediates. However, intricate catalytic behavior of DACs, influenced by their unique interatomic spatial structures, remains elusive and is an ongoing area of inquiry. Herein, for the first time, Pt 1 Fe 1 DACs with a controllable active‐site spatial structure is designed to systematically understand the spatial configurations in regulating the electronic structure and catalytic activity of active sites. Among these, 3D asymmetric coordinated Pt 1 Fe 1 ‐TAC (Pt‐Fe‐N2) dimer catalyst with distinctive interatomic relative spatial structure exhibits superior all‐pH hydrogen evolution reaction (HER) performance due to its strong interatomic interactions and unique electron transfer from Fe to Pt. Operando X‐ray absorption spectroscopy and theoretical calculations reveal that strong inter‐site synergistic interactions enable Pt 1 Fe 1 ‐TAC dimer catalyst with optimized reaction pathway during HER, resulting in high mass activity of 81‐fold increase compared to commercial Pt/C. Besides, an anion exchange membrane water electrolyzer employing Pt 1 Fe 1 ‐TAC dimer catalyst demonstrates 1200 h of stable operation at an industrial‐scale current density of 1000 mA cm −2 with cell voltage of 1.85 V. This research is of great significance for understanding the design of dual atomic sites with controllable spatial positions for efficient hydrogen reactions.