Zhang Xiao-Ling, Ye Ya-Ling, Zhang Li, Li Xiang-Hui, Yu Dan, Chen Jing-Hua, Sun Wei-Ming
Department of Basic Chemistry, The School of Pharmacy, Fujian Medical University, Fuzhou 350108, People's Republic of China.
Phys Chem Chem Phys. 2021 Sep 14;23(34):18908-18915. doi: 10.1039/d1cp01533h. Epub 2021 Aug 23.
Converting earth-abundant nitrogen (N) gas into ammonia (NH) under mild conditions is one of the most important issues and a long-standing challenge in chemistry. Herein, a new superatom CaB was theoretically designed and characterized to reveal its catalytic performance in converting N into NH 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). More importantly, this well-designed superatom possesses unique geometric and electronic features, which can fully activate Nvia a "double-electron transfer" mechanism, and then convert the activated N into NH 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 N to NH.
在温和条件下将地球上储量丰富的氮气（N）转化为氨（NH₃）是化学领域最重要的问题之一，也是一个长期存在的挑战。在此，通过密度泛函理论（DFT）计算，从理论上设计并表征了一种新型超原子CaB₁₂，以揭示其将N₂转化为NH₃的催化性能。该团簇具有类似碱金属的特性，其垂直电离能（VIE，4.29 eV）低于钾（4.34 eV），同时，较大的HOMO-LUMO能隙和每个原子的结合能（E）保证了其高稳定性。更重要的是，这种精心设计的超原子具有独特的几何和电子特征，能够通过“双电子转移”机制充分活化N₂，然后通过一条远端反应途径将活化后的N₂转化为NH₃，其能垒低至0.71 eV。人们乐观地希望这项工作能够激发更多的努力，设计出特定的超原子作为将N₂化学吸附并还原为NH₃的优异催化剂。
