Center for Catalytic Science and Technology, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, USA.
J Chem Phys. 2013 May 7;138(17):174702. doi: 10.1063/1.4803128.
The adsorption of atomic nitrogen on Ni/Pt(111) surface bimetallics has been investigated as a function of the local microstructure of Ni and Pt atoms via density functional theory (DFT) calculations. Microstructures include surface and subsurface Ni atoms on Pt(111) as limiting cases, and also small clusters of Ni in the first and/or second layer of Pt. It is shown that the binding energy of N can be approximated as a perturbation from that on the host metal (Pt) with a linear short-ranged correction from the guest metal (Ni) that accounts for the coordination environment of nitrogen up to the 3rd nearest Ni neighbor. This model is rationalized with the d-band center theory. Coverage effects are also included. The model can be parameterized with a limited number of DFT calculations and applied to other bimetallic catalysts to estimate the coverage dependent binding energy on complex metal microstructures.
通过密度泛函理论（DFT）计算，研究了原子氮在 Ni/Pt(111) 表面双金属上的吸附，作为 Ni 和 Pt 原子局部微观结构的函数。微观结构包括 Pt(111)表面和次表面的 Ni 原子作为极限情况，以及 Pt 第一层和/或第二层中的 Ni 小簇。结果表明，N 的结合能可以近似为来自宿主金属（Pt）的微扰，来自客体金属（Ni）的线性短程校正可以解释氮的配位环境，直至第 3 近邻 Ni 邻居。该模型通过 d 带中心理论进行了合理化。还包括覆盖效应。该模型可以用有限数量的 DFT 计算进行参数化，并应用于其他双金属催化剂，以估计复杂金属微观结构上覆盖度相关的结合能。
