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

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 Pt1 -Ni1 interspace to achieve Pt1 Ni1 dimers and Pt1 +Ni1 heteronuclear dual-single-atom catalysts (HDSACs) by tailoring steric hindrance between metal precursors during synthesis. Spectroscopic characterization reveals obvious electron transfers in Pt1 Ni1 oxo dimers but not in Pt1 +Ni1 HDSAC. In the hydrolysis of ammonia borane (AB), the H2 formation rates show an inverse proportion to the Pt1 -Ni1 interspace. The rate of Pt1 Ni1 dimers is ≈13 and 2 times higher than those of Pt1 and Pt1 +Ni1 HDSAC, manifesting the interspace-dependent synergy. Theoretical calculations reveal that the bridging OH group in Pt1 Ni1 dimers promotes water dissociation, while Pt1 facilitates the cleavage of B-H bonds in AB, which boosts a bifunctional synergy to accelerate H2 production cooperatively.