Structure and Energetics of Graphene Oxide Isomers: Ab Initio Thermodynamic Analysis

TL;DR

This study uses high-level theoretical methods to analyze the thermodynamic stability and electronic structure of various graphene oxide isomers, providing insights for experimental characterization and nanotechnological applications.

Contribution

It offers a detailed ab initio thermodynamic analysis of multiple GO configurations, revealing stability preferences and bonding characteristics not previously detailed.

Findings

Edge positions are more thermodynamically favorable than center or side positions.

All oxygen-containing groups are thermodynamically permitted on GO surface.

Identification of a potentially novel covalent-electrostatic bonding reinforcement in GO.

Abstract

Graphene oxide (GO) holds significant promise for electronic devices and nanocomposite materials. A number of models were proposed for GO structure, combining carboxyl, hydroxyl, carbonyl and epoxide groups at different locations. The complexity and variety of GO isomers, whose thermodynamic stability and formation kinetics depend on applied conditions, make determination of GO structure with atomistic precision challenging. We report high level theoretical investigation of multiple molecular configurations, which are anticipated in GO. We conclude that all oxygen containing groups at the GO surface are thermodynamically permitted, whereas the edge positions are systematically more favorable than the center and side positions. We discuss a potentially novel type of chemical bond or bonding reinforcement in GO, which consists of a covalent bond and a strong electrostatic contribution from a polarized graphene plane. We observe and analyze significant modifications of graphene geometry and electronic structure upon oxidation. The reported thermodynamic data guide experiments aimed at deciphering GO chemical composition and structure, and form the basis for predicting GO properties required for nano-technological applications.