A Ni‐Bonded Hydride in Superatomic Silver Nanoclusters: Probing Synergistic Heteroatomic Core Effects on Oxygen Evolution Reactivity

Abstract In the context of the intensely investigated field of heterometal doping of coinage nanoclusters (NCs), an increasing attention has shifted toward NCs doped with first‐row transition metals due to their economic viability. Herein, the Ni‐Ag bimetallic NCs NiAg 20 S 2 P (O i Pr) 2 12 NiAg 20 and NiHAg 19 S 2 P (O i Pr) 2 12 NiHAg 19 are reported, which are synthesized via a one‐pot reduction method. NiHAg 19 is the first example of an NC containing an encapsulated NiH unit and a rare species exhibiting Ni (0) ─H bonding. The NiAg 20 and NiHAg 19 compositions are confirmed by single‐crystal X‐ray diffraction (SCXRD) and supported by density functional theory (DFT) calculations. Both NCs feature a superatomic 8‐electron count with 1S 2 1P 6 configuration. The effect of nickel‐doping on the oxygen evolution reaction (OER) catalytic performance is investigated. It significantly enhances alkaline OER activity, with NiAg 20 and NiHAg 19 showing improved catalytic performances compared to their monometallic silver counterparts.