Strong and tough graphene papers constructed with pyrene-containing small molecules via π-π/H-bonding synergistic interactions

Lightweight yet strong paper with high toughness is desirable especially for impact protection. Herein we demonstrated electrically conductive and mechanically robust paper (AP/PB-GP) made of reduced graphene oxide via interfacial crosslinking with 1-aminopyrene (AP) and 1-pyrenebutyrat (PB) small molecules. The AP/PB-GP with thickness of over ten micrometer delivers a record-high toughness (∼69.67 ± 15.3 MJ m⁻³ in average), simultaneously with superior strength (close to 1 GPa), allowing an impressive specific penetration energy absorption (∼0.17 MJ kg⁻¹) at high impact velocities when used for ballistic impact protection. Detailed interfacial and structural analysis reveals that the reinforcement is synergistically determined by π-π interaction and H-bonding linkage between adjacent graphene lamellae. Especially, the defective pores within the graphene platelets benefit the favorable adsorption of the pyrene-containing molecules, which imperatively maximizes the interfacial binding, facilitating deflecting crack and plastic deformation under loading. Density functional theory simulation suggests that the coupling between the polar functional groups, e.g., −COOH, at the edges of graphene platelets and −NH₂ and −COOH of AP/PB are critical to the formation of hydrogen bonding network.