Hydrogen Evolution Reactions of Hydrocarbons and Hydroborons Promoted by Superatomic Nbn– Clusters

Hydrogen evolution reactions (HER) are crucial for producing renewable and ecological hydrogen energy. Here we report the finding that ethyl acetylene (C₂H₂), borane (B₂H₆), and benzene (C₆H₆) undergo drastic dehydrogenation reactions upon interaction with niobium cluster anions (Nb_n^–). This finding was enabled by our very sensitive and specialized mass spectrometer, which monitored the cluster ions and the resulting metal carbide and boride products in real time. Through mass spectrometry experiments and density functional theory computations, we delved into the varying reactivities of these common gas molecules with small Nb_n^– clusters and elucidated the underlying reaction mechanisms. These findings shed light on the HER mechanisms of hydrocarbon and hydroboron molecules on superatomic Nb_n^– clusters, furnishing valuable insights pertinent to the advancement of hydrogen energy resources.