Electrides, i.e. salts in which electrons serve as anions, are promising materials for lowering activation energies of chemical reactions. Ab initio simulations are used to investigate the effect of the electron anions in a prototype mayenite-based electride (C12A7:e–) on the mechanism of N2 dissociation. It is found that both atomic and molecular nitrogen species chemisorb on the electride surface and become negatively charged due to the electron transfer from the substrate. However, charging alone is not sufficient to promote dissociation of N2 molecules. In the presence of Ru, N2 adsorbs with the formation of a cis-Ru2N2 complex and the NN bond weakens due to both the electron transfer from the substrate and interaction with Ru. This complex transforms into a more stable trans-Ru2N2 configuration, in which the N2 molecule is dissociated, with the calculated barrier of 116 kJ mol1 and the overall energy gain of 72 kJ mol1. In contrast, in the case of the stoichiometric mayentie, the cis-Ru2N2 is ∼34 kJ mol–1 more stable than the trans-Ru2N2, while the cis–trans transition has a barrier of 192 kJ mol–1. Splitting of N2 is promoted by a combination of the strong electron donating power of C12A7:e–, ability of Ru to capture N2, polarization of Ru clusters, and electrostatic interaction of negatively charged N species with the surface cations
电子晶体，即盐中的电子作为阴离子，是降低化学反应的活化能很有前途的材料。从头计算模拟用于研究在原型基础电极的电子离子钙铝石的效果（C12A7：E–）对N2的解离机理。研究发现，原子和分子的化学吸附在电极表面的氮物种和带负电，由于从基板的电子转移。然而，收费不足以促进N2分子的离解。在钌的存在下，N2吸附一cis-ru2n2复杂和N–N键的削弱由于双方的电子转移从Ru衬底和相互作用形成的。这个复杂的转变为一个更稳定的trans-ru2n2配置，其中N2分子解离，与计算障碍116 kJ/mol和72 kJ/mol–1–1整体的能量增益。相比之下，在化学计量比的情况下的mayentie，cis-ru2n2是∼34 kJ/mol–1比trans-ru2n2更稳定，而CIS–跨过渡192 kJ/mol–1的障碍。分裂氮是通过强给电子能力的提升：E–C12A7，Ru捕捉N2能力，Ru簇的极化，和静电相互作用的带负电荷的氮物种与表面阳离子