Valence Band Structure Engineering in Graphene Derivatives

Engineering of the 2D materials electronic structure is at the forefront of nanomaterials research nowadays, giving an advance in the development of next generation photonic devices, e sensing technologies, and smart materials. Herein, employing core level spectroscopy methods combined with density functional theory DFT modeling, the modification of the graphenes valence band VB upon its derivatization by carboxyls and ketones is revealed. The appearance of a set of localized states in the VB of graphene related to molecular orbitals of the introduced functionalities is signified both experimentally and theoretically. Applying the DFT calculations of the density of states projected on the functional groups, their contributions to the VB structure are decomposed. An empirical approach, allowing one to analyze and predict the impact of a certain functional group on the graphenes electronic structure in terms of examination of the model molecules, mimicking the introduced functionality, is proposed and validated. The interpretation of the arising states origin is made and their designation, pointing out their symmetry type, is proposed. Taken together, these results guide the band structure engineering of graphene derivatives and give a hint on the mechanisms underlying the alteration of the VB structure of 2D materials upon their derivatizatio

Manifesting Epoxide and Hydroxyl Groups in XPS Spectra and Valence Band of Graphene Derivatives

The derivatization of graphene to engineer its band structure is a subject of significant attention nowadays, extending the frames of graphene material applications in the fields of catalysis, sensing, and energy harvesting. Yet, the accurate identification of a certain group and its effect on graphene s electronic structure is an intricate question. Herein, we propose the advanced fingerprinting of the epoxide and hydroxyl groups on the graphene layers via core level methods and reveal the modification of their valence band VB upon the introduction of these oxygen functionalities. The distinctive contribution of epoxide and hydroxyl groups to the C 1s X ray photoelectron spectra was indicated experimentally, allowing the quantitative characterization of each group, not just their sum. The appearance of a set of localized states in graphene s VB related to the molecular orbitals of the introduced functionalities was signified both experimentally and theoretically. Applying the density functional theory calculations, the impact of the localized states corresponding to the molecular orbitals of the hydroxyl and epoxide groups was decomposed. Altogether, these findings unveiled the particular contribution of the epoxide and hydroxyl groups to the core level spectra and band structure of graphene derivatives, advancing graphene functionalization as a tool to engineer its physical propertie