Exploring Nitrogen-Mediated Effects on Fe and Cu Cluster Development in Graphene: A DFT Study.

Abstract

The controlled growth and stability of transition metal clusters on N-doped materials have become the subject of intense investigation for unveiling comprehension on the cluster growth evolution. In this study, we investigated the growth mechanisms of non-magnetic (copper) and magnetic (iron) clusters on graphene with two atomic vacancies, with and without pyridinic nitrogen (N). Our results determine the role of pyridinic N in the growth, and physicochemical properties of the mentioned metal clusters. In an N environment, Cu grows perpendicularly, whereas in N-deficient conditions, the cluster agglomerates. The Fe cumulate-type clusters are formed regardless of the presence of N. However, N causes the Fe cluster to rise over one side of the surface without deforming the monolayer; meanwhile, in the absence of N, the Fe cluster protrudes from both sides of the monolayer. Remarkably, the N presence makes feasible to induce magnetization in the Cun N4V2 systems and aid focalizing the magnetic properties on the Fe cluster for the Fen N4V2 case. These findings offer insights into the role of N in cluster growth, with potential implications for diverse applications, including magnetic and electrocatalytic materials.