A Review on Pre-, In-Process, and Post-Synthetic Strategies to Break the Surface Area Barrier in g-C₃N₄ for Energy...

Nanomaterials with large specific surface area (SSA) have emerged as pivotal platforms for energy storage and environmental remediation, primarily due to their enhanced active site exposure, improved mass transport capabilities, and superior interfacial reactivity. Among them, polymeric carbon nitride (g-C₃N₄) has garnered significant attention in energy and environmental applications owing to its visible-light-responsive bandgap (~2.7 eV), exceptional thermal/chemical stability, and earth-abundant composition. However, the practical performance of g-C₃N₄ is fundamentally constrained by intrinsic limitations, including its inherently low SSA (<20 m²/g via conventional thermal polymerization), rapid recombination of photogenerated carriers, and inefficient charge transfer kinetics. Notably, the theoretical SSA of g-C₃N₄ reaches 2500 m²/g, yet achieving this value remains challenging due to strong interlayer van der Waals interactions and structural collapse during synthesis. Recent advances demonstrate that state-of-the-art strategies can elevate its SSA to 50-200 m²/g. To break this surface area barrier, advanced strategies achieve SSA enhancement through three primary pathways: pre-treatment (molecular and supramolecular precursor design), in process (templating and controlled polycondensation), and post-processing (chemical exfoliation and defect engineering). This review systematically examines controllable synthesis methodologies for high-SSA g-C₃N₄, analyzing how SSA amplification intrinsically modulates band structures, extends carrier lifetimes, and boosts catalytic efficiencies. Future research should prioritize synergistic multi-stage engineering to approach the theoretical SSA limit (2500 m²/g) while preserving robust optoelectronic properties.