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 BÀ H bonds in AB, which boosts a bifunctional synergy to accelerate H 2 production cooperatively.

A Ru atomic cluster-installed Co–Co2B nanocatalyst remarkably combats product inhibition while sustaining high turnover frequency of hydrogen production

“…Few reports on using supported catalysts with vacancies that favor the dissolution of borates are known in the literature. 32–34 Several catalysts comprising non-noble metals, 35–37 noble metals, 38–41 alloys, 42–45 borides, 46–48 phosphides, 49–53 nitrides, 54 single-atom catalysts, 55–57 and newer designs 36,58,59 have also been reported for the production of hydrogen from AB via hydrolysis 35–37 or methanolysis having appreciable rates. 41,48,60 However, effectively combating product inhibition by the catalyst in concurrence with a steep enhancement of catalytic efficiency and maintaining it throughout the catalytic cycle is unexplored because of the challenges associated with designing such catalysts.…”