Designing an alkali-metal-like superatom Ca3B for ambient nitrogen reduction to ammonia. Issue 34 (23rd August 2021) - Zhang, Xiao-Ling
Abstract : An alkali-metal-like superatom Ca3 B was theoretically designed and further used as a potential catalyst for nitrogen reduction under mild conditions. Abstract : Converting earth-abundant nitrogen (N2 ) gas into ammonia (NH3 ) under mild conditions is one of the most important issues and a long-standing challenge in chemistry. Herein, a new superatom Ca3 B was theoretically designed and characterized to reveal its catalytic performance in converting N2 into NH3 by means of density functional theory (DFT) computations. The alkali-metal-like identity of this cluster is verified by its lower vertical ionization energy (VIE, 4.29 eV) than that of potassium (4.34 eV), while its high stability was guaranteed by the large HOMO–LUMO gap and binding energy per atom ( E b ). More importantly, this well-designed superatom possesses unique geometric and electronic features, which can fully activate N2 via a "double-electron transfer" mechanism, and then convert the activated N2 into NH3 through a distal reaction pathway with a small energy barrier of 0.71 eV. It is optimistically hoped that this work could intrigue more endeavors to design specific superatoms as excellent catalysts for the chemical adsorption and reduction of N2 to NH3 .