Changes in the structure and properties of graphene oxide surfaces during reduction and modification

Abstract

The aim of the current study was to find changes in the structure and state of the surface of graphene oxide (GO) under the conditions of its reduction and modification by hetero atoms of nitrogen and amino acids. Reduction of GO was performed with hydrazine hydrate (R-GO), doping with nitrogen atoms - urea impregnation and subsequent heat treatment (N-GO), and the surface of GO was modified with sulfur-containing amino acid – L-cysteine by nucleophilic addition (L-GO). The samples obtained were characterized by analytical methods, such as Raman scattering, IR spectroscopy, TPD-mass-spectrometry, dynamic light scattering spectroscopy. The available Raman spectra indicate a defective structure of GO, reduction of GO leads to greater ordering of the structure in relation to GO, nitrating and modification by amino acid - to the opposite effect, a slight deterioration of the structural state. According to the results of IR spectroscopy, also confirmed by TPD-MS, GO has a large number of functional surface groups: (OH), (C=O), (C=C), (C-O-C), (CO-O-CO), (CH). Hydrazine reduction completely hydrophobizes the surface, in the IR spectra there is only a peak at ~ 1040 cm–1, which corresponds to CO-O-CO vibrations, with significantly reduced intensity, as well as bands at 2120 and 2300 cm–1, which indicate the aromatic nature of the samples and exist in all GO derivatives. In nitrogen and sulfur-containing samples (L-GO) a new peak of ~ 1520 cm–1appears, which corresponds to N-H vibrations in amines. Sulfur-containing derivatives have valence vibrations at 600 cm–1, which most likely corresponds to S-H bonds. Thus, modification of GO leads to a significant change in its structure and surface chemistry, which in turn affects the capability of the obtained samples to capture free radicals. Previous empirical studies have shown that this property increases in the series L-GO > GO > N-GO > R-GO.