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Adjacent-Site Proximity as a Dominant Activity Descriptor in Single-Atom Pt Catalysts for Hydrogen Evolution Reaction
Xue-Lu Chen1, Yu-Yang Liu2, Sudip Biswas1
1State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, People's Republic of China.
None:
Precise control of adjacent-site proximity and electronic states in single-atom catalysts (SACs) enable atomic-level modulation of intrinsic catalytic properties. While the influence of electronic structure on catalytic performance is well established, the impact of adjacent-site proximity remains underexplored. Here, we report the single-atom platinum catalysts on MoS2 (Pt-SAC/MoS2), in which both the controlled enrichment of adjacent Pt (Ptadj) sites and the Pt oxidation state are tuned via galvanic displacement of underpotentially deposited Cu adatoms. We find that hydrogen evolution reaction (HER) activity is predominantly governed by non-bonded Pt∙∙∙Pt proximity rather than oxidation state: enriched Ptadj sites in PtSA-0.1/MoS2 exhibits a mass activity 41-fold higher than isolated Pt (Ptiso) sites in PtSA-0.3/MoS2 under acidic conditions. In situ infrared spectroscopy reveals that Ptiso sites preferentially bind linear adsorbed hydrogen intermediate (*HL), whereas Ptadj sites stabilize bridge hydrogen intermediate (*HB), which is indicative of adjacent-site proximity. Density functional theory calculations reveal that neighboring Pt atoms promote the formation of a three-center "Pt-H-Pt" bonding intermediate, which lowers the H-H coupling barrier and accelerates HER kinetics. These findings establish adjacent-site proximity as a dominant activity descriptor in SACs and provide new design principles for next-generation high-performance electrocatalysts.
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