The allure of metal-free semiconductors with narrow bandgaps has captured significant attention in recent decades, proving exceptionally versatile for various electronic applications such as infrared devices, light-emitting diodes, electrocatalysts, and thermo-photovoltaics. This interest has been further fueled by the emergence of two-dimensional nanomaterials in material science and engineering following the groundbreaking discovery of graphene by a collaborative effort in the past decade . Recently, a breakthrough occurred with the experimental realization of a single-crystal 2D carbon material, termed monolayer quasi-hexagonal-phase fullerene (C 60 ), boasting a semiconducting bandgap of approximately 1.6 eV . This achievement addresses the issue of null bandgaps observed in other 2D carbonbased materials. Using an organic cation slicing strategy, researchers exfoliated quasi-hexagonal bulk single crystals to obtain monolayer polymeric C 60 . Using an interlayer bonding cleavage strategy, they obtained large-sized C 60 2D crystals. These crystals exhibit a unique structure where C 60 polymers form covalently bonded cluster cages within a plane. This clustering mechanism led to the formation of two stable crystals, namely closely packed quasi-hexagonal (qHP C 60 ) and quasi-tetragonal (qTP C 60 ) phases . Monolayer C 60 distinguishes itself from other 2D materials due to its larger surface area and increased active sites resulting from the quasi-0D network structures of C 60 cages. It exhibits excellent thermodynamic stability and high carrier mobility, making it a promising candidate for photocatalytic water splitting . Obtaining monolayer polymeric C60 involved an organic cation slicing strategy, yielding substantial-sized C 60 2D crystals with remarkable crystallinity and thermodynamic stability. Further exploration in these areas holds significant potential to unlock their full capabilities. Notably, Gao and colleagues' first-principles findings suggest that N-C 60 fullerene could serve as a promising cathode catalyst for hydrogen fuel cells by facilitating the water formation reaction without encountering activation energy barriers . Despite valuable insights from previous research, a comprehensive understanding of their electronic, optical, and mechanical characteristics is still awaited. Peng and his team recently discovered that using a weakly screened hybrid functional in conjunction with time-dependent Hartree-Fock calculations can accurately reproduce the experimentally measured optical band gap of the monolayer of C 60 . The various phases of monolayer fullerene networks feature suitable band gaps, displaying high carrier mobility and appropriate band edges. These characteristics render them thermodynamically favourable for driving overall water splitting . The deliberate choice of foreign elements in carbon-based 2D materials, ensuring an optimal carbon-to-doping element ratio, is crucial for customizing the electronic properties of these newly developed 2D materials. This process enhances their suitability for advanced device applications . Various methods have emerged to refine nanomaterials' properties, such as surface defects, metal decoration, and transition metal doping. These approaches are extensively investigated through both experimental studies and DFT-based calculations. This understanding presents intriguing opportunities for customizing nanomaterials to fulfil the specific needs across various scientific and engineering domains .