Intrinsic self-healing materials have received significant attention due to the characteristic recovery after damage properties through reversible dynamic covalent and non-covalent interactions. Furthermore, functional recovery with reliable mechanical properties are highly keen as protective coatings, specifically for devices and sensors vulnerable to abrasion in severe environments. Here, we present a functional hierarchical nanostructure capable of multiple micro-sized healings, with enhanced mechanical hardness due to the incorporation of graphene oxide (rGO) nanoplatelets. A self-healing multilayered nanocomposite formed by poly(ethylene imine) (PEI) and poly(acrylic acid) (PAA) was easily assembled by the layer-by-layer (LbL) technique. The addition of the rGO nanoplatelets in the LbL nanostructure resulted in a 13-fold increase in hardness (0.4 ± 0.1 GPa) when compared to the (PEI/PAA) architecture (0.03 ± 0.01 GPa). In addition, the nanocomposite presents an enhanced insulating electrical behavior (∼ 4.10⁻⁸ S/cm) despite the addition of the rGO nanoplatelets. Raman and Zeta Potential analysis indicated a possible wrapping of the rGOs by PEI, justifying the observed insulating electrical characteristics. The nanocomposite presents good hydrophobicity with a water contact angle of 136°, interesting to extend the lifetime and protect underlying layers from humidity, degradation, and encrustation. Therefore, we propose an attractive hydrophobic, electrically insulating, and mechanically resistant multifunctional coating for high-performance electronic interfaces from minor cuts and abrasions, dispensing maintainer intervention.

Graphene is a breakthrough 2D material due to its unique mechanical, electrical, and thermal properties, with considerable responsiveness in real applications. However, the coverage of large areas with pristine graphene is a challenge and graphene derivatives have been alternatively exploited to produce hybrid and composite materials that allow for new developments, considering also the handling of large areas using distinct methodologies. For electronic applications there is significant interest in the investigation of the electrical properties of graphene derivatives and related composites to determine whether the characteristic 2D charge transport of pristine graphene is preserved. Here, we report a systematic study of the charge transport mechanisms of reduced graphene oxide chemically functionalized with sodium polystyrene sulfonate (PSS), named as GPSS. GPSS was produced either as quantum dots (QDs) or nanoplatelets (NPLs), being further nanostructured with poly(diallyldimethylammonium chloride) through the layer-by-layer (LbL) assembly to produce graphene nanocomposites with molecular level control. Current-voltage (I-V) measurements indicated a meticulous growth of the LbL nanostructures onto gold interdigitated electrodes (IDEs), with a space-charge-limited current dominated by a Mott-variable range hopping mechanism. A 2D intra-planar conduction within the GPSS nanostructure was observed, which resulted in effective charge carrier mobility (μ) of 4.7 cm² V^-1 s^-1 for the QDs and 34.7 cm² V^-1 s^-1 for the NPLs. The LbL assemblies together with the dimension of the materials (QDs or NPLs) were favorably used for the fine tuning and control of the charge carrier mobility inside the LbL nanostructures. Such 2D charge conduction mechanism and high μ values inside an interlocked multilayered assembly containing graphene-based nanocomposites are of great interest for organic devices and functionalization of interfaces.