As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and "earth-abundant" nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The construction and characteristics of each classification of the heterojunction system will be critically reviewed, namely metal-g-C3N4, semiconductor-g-C3N4, isotype g-C3N4/g-C3N4, graphitic carbon-g-C3N4, conducting polymer-g-C3N4, sensitizer-g-C3N4, and multicomponent heterojunctions. The band structures, electronic properties, optical absorption, and interfacial charge transfer of g-C3N4-based heterostructured nanohybrids will also be theoretically discussed based on the first-principles density functional theory (DFT) calculations to provide insightful outlooks on the charge carrier dynamics. Apart from that, the advancement of the versatile photoredox applications toward artificial photosynthesis (water splitting and photofixation of CO2), environmental decontamination, and bacteria disinfection will be presented in detail. Last but not least, this comprehensive review will conclude with a summary and some invigorating perspectives on the challenges and future directions at the forefront of this research platform. It is anticipated that this review can stimulate a new research doorway to facilitate the next generation of g-C3N4-based photocatalysts with ameliorated performances by harnessing the outstanding structural, electronic, and optical properties for the development of a sustainable future without environmental detriment.
Photocatalysis is a perennial solution that promises to resolve deep-rooted challenges related to environmental pollution and energy deficit through harvesting the inexhaustible and renewable solar energy. To date, a cornucopia of photocatalytic materials has been investigated with the research wave presently steered by the development of novel, affordable, and effective metal-free semiconductors with fascinating physicochemical and semiconducting characteristics. Coincidentally, the recently emerged red phosphorus (RP) semiconductor finds itself fitting perfectly into this category ascribed to its earth abundant, low-cost, and metal-free nature. More notably, the renowned red allotrope of the phosphorus family is spectacularly bestowed with strengthened optical absorption features, propitious electronic band configuration, and ease of functionalization and modification as well as high stability. Comprehensively detailing RP's roles and implications in photocatalysis, this review article will first include information on different RP allotropes and their chemical structures, followed by the meticulous scrutiny of their physicochemical and semiconducting properties such as electronic band structure, optical absorption features, and charge carrier dynamics. Besides that, state-of-the-art synthesis strategies for developing various RP allotropes and RP-based photocatalytic systems will also be outlined. In addition, modification or functionalization of RP with other semiconductors for promoting effective photocatalytic applications will be discussed to assess its versatility and feasibility as a high-performing photocatalytic system. Lastly, the challenges facing RP photocatalysts and future research directions will be included to propel the feasible development of RP-based systems with considerably augmented photocatalytic efficiency. This review article aspires to facilitate the rational development of multifunctional RP-based photocatalytic systems by widening the cognizance of rational engineering as well as to fine-tune the electronic, optical, and charge carrier properties of RP.