Novel Graphene-Gold Hybrid Nanostructures Constructed via Sulfur Modified Graphene: Preparation and Characterization by Surface and Electrochemical Techniques

• A new hybrid of GNs-AuNPs is synthesized by using sulfur-modified graphene.
• Stability of the hybrid is exceptionally improved in comparison with previous works.
• Aminothiophenol mediated fabrication and stabilization of GNs-AuNPs on GCE electrode.
• High electrocatalytic activity was observed for O2 reduction by hybrid.
• Activity of the hybrid was originated from synergistic effect and surface roughness.

A novel and uniform graphene nanosheet-gold nanoparticles (GNs-AuNPs) hybrid has been fabricated from sulfur-modified graphene nanosheets (S-GNs) impregnated with HAuCl4 as Au precursor. Physicochemical and morphological characteristics of the GNs-AuNPs hybrids were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), surface Raman spectroscopy (SRS), and high resolution transmission electron microscopy (HRTEM). The results of the XRD and HRTEM demonstrated well dispersed Au nanoparticles on GNs with an average particle size of less than 10 nm and a narrow size distribution of 6 to 8 nm. A film of GNs-AuNPs hybrid was constructed on a glassy carbon electrode (GCE) through layer-by-layer (LBL) assembly of 4-aminothiphenol (ATP) on GCE, and then, transferring the hybrid to the sulfur function of ATP to form GCE-ATP-GNs-AuNPs modified surface. Application of the GNs-AuNPs hybrid in electrochemical biosensing was demonstrated by immobilization of glucose oxidase (GOx) as a model on the surface of GCE-ATP-GNs-AuNPs, and then, using it for sensing of glucose. The biosensor exhibited a wide linear response range, from 1.0 to 12.0 mM and 0.1 to 8.0 mM glucose, with a detection limit of 9.3 and 4.1 μM and high sensitivity, 47.6 μA mM−1 cm−2 and 45.0 kΩ/log(Cglucose/mM) obtained by voltammetry and electrochemical impedance spectroscopy (EIS), respectively. According to the results obtained by analysis of the EIS experimental data, the source of enhanced activity was found to be originated from the synergistic effect of GNs and AuNPs, the role of ATP mediating assembling of GNs-AuNPs hybrid on GCE, and the increase in the surface roughness. This work opens up a new and facile way for direct preparation of metal nanoparticles embedded in GNs, which will enable exciting opportunities in advanced applications based on graphene-metal hybrids like electrocatalysis for energy conversion and highly sensitive modifier films for electrochemical sensors and biosensors.

Graphene nanosheet-gold nanoparticles (GNs-AuNPs) hybrid has been fabricated from sulfur-modified graphene nanosheets (S-GNs) impregnated with HAuCl4 as Au precursor. Application of the GNs-AuNPs hybrid in electrochemical biosensing was demonstrated by immobilization of glucose oxidase as a model on the surface of GCE-ATP-GNs-AuNPs, and then, using it for sensing of glucose.Figure optionsDownload as PowerPoint slide