Methane activation is a pivotal step in the application of natural gas converting into high-value added chemicals via methane steam/dry reforming reactions. Ni element was found to be the most widely used catalyst. In present work, methane activation on MgO supported Ni-M (M = Fe, Co, Cu, Pd, Pt) cluster was explored through detailed density functional theory calculations, compared to pure Ni cluster. CH₄ adsorption on Cu promoted Ni cluster requires overcoming an energy of 0.07 eV, indicating that it is slightly endothermic and unfavored to occur, while the adsorption energies of other promoters M (M = Fe, Co, Pd and Pt) are all higher than that of pure Ni cluster. The role of M on the first C-H bond cleavage of CH₄ was investigated. Doping elements of the same period in Ni cluster, such as Fe, Co and Cu, for C-H bond activation follows the trend of the decrease of metal atom radius. As a result, Ni-Fe shows the best ability for C-H bond cleavage. In addition, doping the elements of the same family, like Pd and Pt, for CH₄ activation is according to the increase of metal atom radius. Consequently, C-H bond activation demands a lower energy barrier on Ni-Pt cluster. To illustrate the adsorptive dissociation behaviors of CH₄ at different Ni-M clusters, the Mulliken atomic charge was analyzed. In general, the electron gain of CH₄ binding at different Ni-M clusters follows the sequence of Ni-Cu (−0.02 e) < Ni (−0.04 e) < Ni-Pd (−0.08 e) < Ni-Pt (−0.09 e) < Ni-Co (−0.10 e) < Ni-Fe (−0.12 e), and the binding strength between catalysts and CH₄ raises with the CH₄ electron gain increasing. This work provides insights into understanding the role of promoter metal M on thermal-catalytic activation of CH₄ over Ni/MgO catalysts, and is useful to interpret the reaction at an atomic scale.

甲烷活化是应用天然气通过甲烷蒸汽/干重整反应转化为高附加值化学品的关键步骤。Ni元素被发现是最广泛使用的催化剂。在目前的工作中，与纯 Ni 簇相比，通过详细的密度泛函理论计算探索了 MgO 负载的 Ni-M（M = Fe、Co、Cu、Pd、Pt）簇上的甲烷活化。Cu促进的Ni簇对CH ₄的吸附需要克服0.07 eV的能量，表明它是轻微吸热的，不利于发生，而其他促进剂M（M = Fe、Co、Pd和Pt）的吸附能均高于纯镍簇。_{M在CH 4}的第一个CH键断裂中的作用进行了调查。在Ni团簇中掺杂Fe、Co、Cu等同期元素对CH键活化的作用遵循金属原子半径减小的趋势。结果，Ni-Fe显示出最好的CH键断裂能力。此外，掺杂同族元素，如Pd和Pt，激活CH ₄是根据金属原子半径的增加。因此，CH 键活化需要 Ni-Pt 簇上的较低能垒。为了说明 CH ₄在不同 Ni-M 簇上的吸附解离行为，分析了 Mulliken 原子电荷。一般来说，CH _{4的电子增益}在不同 Ni-M 簇上的结合遵循 Ni-Cu (-0.02 e) < Ni (-0.04 e) < Ni-Pd (-0.08 e) < Ni-Pt (-0.09 e) < Ni-Co (- 0.10 e) < Ni-Fe (-0.12 e)，催化剂与CH ₄的结合强度随着CH ₄电子增益的增加而提高。_{这项工作为理解助催化剂金属 M 在 Ni/MgO 催化剂上对 CH 4}的热催化活化的作用提供了见解，并有助于在原子尺度上解释反应。