▎ 摘　　要

Electroactivity of graphene-family nanomaterials and three-dimensional porous architectures is key for various applications at the grand challenges of "energy-water-sensing nexus." It requires well-controlled morphology, manipulation of surface chemistry, interconnected topologic network, as well as electronic properties. Here, we demonstrate by taking advantage of hierarchical mesoporosity, optimized defects number density, n(D) (edges-plane and pore sites, oxygenated and nitrogenated functionalities), further invoked by synergistic coupling between one-dimensional single-walled carbon nanotube (SWCNT) as "nano" spacers and polymer linker with two-dimensional reduced graphene oxide derived three-dimensional scaffolds (known as aerogels) under hydrothermal conditions, and improved electrochemical (re) activity by enhancing the heterogeneous electron transfer rate (k(ET)). We determined the correlation among n(D), in-plane sp(2)C cluster, L-a and interdefect distance, LD (all via Raman spectroscopy), and k(ET) (via scanning electrochemical microscopy) to establish "structure-property-functionality- electroactivity" relationships. The prominent Raman bands were also analyzed to determine the sp(2)-bonded C cluster size (L-a) for graphene- and nanotube-rich phases. The interplay of (1) rich surface redox chemistry due to carbonyl-C=O, carboxyl-COOH, pryridinic-N and pyrrolic-N functional groups, and geometric defects; (2) protruded edge plane and nanopores sites; (3) topological network; and (4) finite density of states with increased vacancy sites is emphasized and signifies the inherently activated electronic states in functionalized nanoporous composite carbon aerogels, for improved physicochemical processes (following graphene < N-graphene < graphene-SWCNT < N-graphene-SWCNT aerogels) relevant for electrocatalysis, thermo-electrochemical energy harvesting, desalination, and biosensing. Published under license by AIP Publishing.