Improving strength and toughness of graphene film through metal ion bridging

The fangs, jaws, and mandibles of marine invertebrates such as Chiton and Glycera show excellent mechanical properties, which are mostly contributed to the interactions between metal (Fe, Cu, Zn, etc.) and oxygen-containing functional groups in proteins. Inspired by these load-bearing skeletal biomaterials, we improved tensile strength and toughness of graphene films through bridging graphene oxide (GO) nanosheets by metal ions. By optimizing the metal coordination form and density of cross-linking network. We revealed the relationship between mechanical properties and the unique spatial geometry of the GO nanosheets bridged by different valence metal ions. The results demonstrated that the divalent metal ions form tetrahedral geometry with carboxylate groups on the edges of the GO nanosheets, and the bond energy is relatively low, which is helpful for improving the toughness of resultant graphene films. While the trivalent metal ions are easily to form octahedral geometry with the GO nanosheets with higher bond energy, which is better for enhancing the tensile strength of graphene films. After reduction, the reduced GO (rGO) film bridged by divalent metal ions shows 43% improvement in toughness, while the rGO film bridged by trivalent metal ions shows 64% improvement in tensile strength. Our work reveals the mechanism of metal coordination bond energy and spatial geometry to improve the mechanical properties of graphene films, which lays a theoretical foundation for improving the tensile strength and toughness of resultant graphene films, and provides an avenue for fabricating high-performance graphene films and other two-dimensional nanocomposites.