Construction of a Self-Assembled Polyelectrolyte/Graphene Oxide Multilayer Film and Its Interaction with Metal Ions

In this study, a composite multilayer film onto gold was constructed from two charged building blocks, i.e., negatively charged graphene oxide (GO) and a branched polycation (polyethylenimine, PEI) via layer-by-layer (LbL) self-assembly technology, and this process was monitored in situ with quartz crystal microbalance (QCM) under different experimental conditions. This included the differences in frequency (Δf) as well as the changes in dissipation to yield information on the absorbed mass and viscoelastic properties of the formed PEI/GO multilayer films. The experimental conditions were optimized to obtain a high amount of the adsorbed mass of the self-assembled multilayer film. The surface morphology of the PEI/GO multilayer film onto gold was studied with atomic force microscopy (AFM). It was found that the positively charged PEI chains were combined with the oppositely charged GO to form an assembled film on the QCM sensor surface, in a wrapped and curled fashion. Raman and UV-vis spectra also showed that the intensities of the GO-characteristic signals are almost linearly related to the layer number. To explore the films for their use in divalent ion detection, the frequency response of the PEI/GO multilayer-modified QCM sensor to the exposure of aqueous solutions solution of Cu²⁺, Ca²⁺, Zn²⁺, and Sn²⁺ was further studied using QCM. Based on the Sauerbrey equation and the weight of different ions, the number of metal ions adsorbed per unit area on the surface of QCM sensors was calculated. For metal ion concentrations of 40 ppm, the adsorption capacities per unit area of Cu²⁺, Zn²⁺, Sn²⁺, and Ca²⁺ were found to be 1.7, 3.2, 0.7, and 4.9 nmol/cm², respectively. Thus, in terms of the number of adsorbed ions per unit area, the QCM sensor modified by PEI/GO multilayer film shows the largest adsorption capacity of Ca²⁺. This can be rationalized by the relative hydration energies.