Selective engineering of oxygen-containing functional groups using the alkyl ligand oleylamine for revealing the luminescence mechanism of graphene oxide quantum dots

Abstract

Oxygen-containing functional groups such as epoxy, hydroxyl, carboxylic, and carboxyl groups have a great influence on the luminescence properties of graphene oxide quantum dots (GOQDs). Understanding their roles is essential for the design and optimization of GOQD performance. Herein, we investigate the effect of epoxide functional groups in GOQDs on the luminescence mechanism through passivation of the epoxide functional groups using the alkyl ligand oleylamine. Luminescence in the as-synthesized GOQDs has two separate origins: intrinsic states derived from localized sp² carbon subdomains and extrinsic states formed by oxygen-functional groups. When the oleylamine ligand is conjugated on the GOQDs, intrinsic PL emission from the localized sp² carbon subdomains decreases. This is discussed in detail, based on optical characterization and first-principles density functional theory calculations, which reveal that the role of the epoxide functional groups is to form localized sp² carbon subdomains emitting intrinsic PL. To the best of our knowledge, this is the first investigation of the role of epoxide functional groups on the luminescence mechanism in GOQDs.