Dehydrogenation of Ammonia Borane by Platinum‐Nickel Dimers: Regulation of Heteroatom Interspace Boosts Bifunctional Synergetic Catalysis

Abstract Regulation of the atom‐atom interspaces of dual‐atom catalysts is essential to optimize the dual‐atom synergy to achieve high activity but remains challenging. Herein, we report an effective strategy to regulate the Pt 1 ‐Ni 1 interspace to achieve Pt 1 Ni 1 dimers and Pt 1 +Ni 1 heteronuclear dual‐single‐atom catalysts (HDSACs) by tailoring steric hindrance between metal precursors during synthesis. Spectroscopic characterization reveals obvious electron transfers in Pt 1 Ni 1 oxo dimers but not in Pt 1 +Ni 1 HDSAC. In the hydrolysis of ammonia borane (AB), the H 2 formation rates show an inverse proportion to the Pt 1 ‐Ni 1 interspace. The rate of Pt 1 Ni 1 dimers is ≈13 and 2 times higher than those of Pt 1 and Pt 1 +Ni 1 HDSAC, manifesting the interspace‐dependent synergy. Theoretical calculations reveal that the bridging OH group in Pt 1 Ni 1 dimers promotes water dissociation, while Pt 1 facilitates the cleavage of B−H bonds in AB, which boosts a bifunctional synergy to accelerate H 2 production cooperatively.