Associative behaviour and effect of functional groups on the fluorescence of graphene oxide

We have juxtaposed the structural, vibrational and emission properties of graphene oxide (GO) with various degrees of reduction with and without a model dispersant, unveiling a strong associative behavior between GO sheets and the influence of H-bonds. The interlayer spacings are similar to 0.84 and 0.78 nm for the as prepared and reduced samples. -OH groups are predominantly effected by the photo-thermal reduction. Also we note some regeneration of > C=O and -COOH groups in reduced samples. Clear changes to the phonon density of states indicated the doping effects due to H-bonds via the oxygeneous groups. Importantly, the defect related Raman bands are rather prone to the effect of dispersant, unveiling their intrinsic nature. In the context of fluorescence, internal vibration relaxation mediated by CC stretch vibrations emphasized the localized nature of sp(2) domains of relatively smaller size. Fluorescence consists of 6 components, where the higher energy components are more influenced due to H-bonds than those of the lower energy regime, attributed to their associative behavior and chemical functionality, respectively. Excitation dependent fluorescence measurements indicated a range of optical gaps from similar to 3.5 to 2 eV. The associative behavior of GO and rGO with and without a dispersant provides crucial insights into the fundamental understanding of various molecular processes.