Adsorption Affinities of Small Volatile Organic Molecules on Graphene Surfaces for Novel Nanofiller Design: A DFT Study

The adsorption of organic molecules on graphene surfaces is a crucial process in many different research areas. Nano-sized carbon allotropes, such as graphene and carbon nanotubes, have shown promise as fillers due to their exceptional properties, including their large surface area, thermal and electrical conductivity, and potential for weight reduction. Surface modification methods, such as the “pyrrole methodology”, have been explored to tailor the properties of carbon allotropes. In this theoretical work, an ab initio study based on Density Functional Theory is performed to investigate the adsorption process of small volatile organic molecules (such as pyrrole derivatives) on graphene surface. The effects of substituents, and different molecular species are examined to determine the influence of the aromatic ring or the substituent of pyrrole’s aromatic ring on the adsorption energy. The number of atoms and presence of π electrons significantly influence the corresponding adsorption energy. Interestingly, pyrroles and cyclopentadienes are 10 kJ mol(−1) more stable than the corresponding unsaturated ones. Pyrrole oxidized derivatives display more favorable supramolecular interactions with graphene surface. Intermolecular interactions affect the first step of the adsorption process and are important to better understand possible surface modifications for carbon allotropes and to design novel nanofillers in polymer composites.