Hydrogen Evolution\nReactions of Hydrocarbons and Hydroborons\nPromoted by Superatomic Nb<sub><i>n</i></sub><sup>–</sup> Clusters

Hydrogen evolution reactions (HER) are crucial for producing\nrenewable\nand ecological hydrogen energy. Here we report the finding that ethyl\nacetylene (C<sub>2</sub>H<sub>2</sub>), borane (B<sub>2</sub>H<sub>6</sub>), and benzene (C<sub>6</sub>H<sub>6</sub>) undergo drastic\ndehydrogenation reactions upon interaction with niobium cluster anions\n(Nb<sub><i>n</i></sub><sup>–</sup>). This finding\nwas enabled by our very sensitive and specialized mass spectrometer,\nwhich monitored the cluster ions and the resulting metal carbide and\nboride products in real time. Through mass spectrometry experiments\nand density functional theory computations, we delved into the varying\nreactivities of these common gas molecules with small Nb<sub><i>n</i></sub><sup>–</sup> clusters and elucidated the underlying\nreaction mechanisms. These findings shed light on the HER mechanisms\nof hydrocarbon and hydroboron molecules on superatomic Nb<sub><i>n</i></sub><sup>–</sup> clusters, furnishing valuable\ninsights pertinent to the advancement of hydrogen energy resources.