Abstract
This study explored the fundamental chemical intricacies behind the interactions between metal catalysts and carbon supports with graphitic nitrogen defects. These interactions were probed by examining metal adsorption, specifically, the location of adsorption and the electronic structure of metal catalysts as the basis for the metal-support interactions (MSIs). A computational framework was developed, and a series of 12 transition metals was systematically studied over various graphene models with graphitic nitrogen defect(s). Different modeling approaches served to provide insights into previous MSI computational discrepancies, reviewing both truncated and periodic graphene models. The computational treatment affected the magnitudes of adsorption energies between the metals and support; however, metals generally followed the same trends in their MSI. It was found that the addition of the nitrogen dopant improved the MSI by promoting electronic rearrangement from the metals' d- to s-orbitals for greater orbital overlap with the carbon support, shown with increased favorable adsorption. Furthermore, the study observed periodic trends that were adept descriptors of the MSI fundamental chemistries.