In situ observation of metal ion interactions with graphene oxide layers: From the growth of metal hydroxide to metal oxide formation

Abstract

The interactions between metal ions and graphene oxide (GO) nanosheets were investigated by in situ two-dimensional grazing incidence X-ray diffraction (GIXRD). We found that metal cations (Mn2+, Co2+, Cu2+, Fe3+) and GO can self-assemble into a hydroxide/GO superlattice by drop-casting a metal chloride and GO solution due to the electrostatic interactions between the positively charged hydroxide and the negatively charged GO nanosheets and the interlayer spacing of the superlattice can be controlled by the cation species. Moreover, based on this superlattice template, graphene-based metal oxide nanosheets can be facilely obtained by subsequent annealing. The growth mechanism and structural evolution of the GO/cation systems can be described in four stages: (1) hydrated cation intercalation of the GO interlayer in an aqueous solution; (2) metal hydroxide growth between the GO layers during annealing, with the formation of a superlattice structure at approximately 250 °C; (3) metal oxide nucleation between the reduced GO (rGO) interlayers with increasing temperature; and (4) complete graphene layer decomposition at a temperature of 600 °C, along with metal oxide nanosheet formation. This work gives a new perspective for understanding the interactions between and growth behaviour of metal cations and GO.