Green, Sustainable, and Multifunctional Biobased Hybrid Nanocomposites: Semiconducting Materials with Tunable Molecular Interfaces for Photocatalysis.

Biobased hybrid semiconducting composites are attracting significant attention as sustainable alternatives to traditional inorganic photocatalysts for environmental remediation and energy-related applications. Recent research progress in biobased hybrid photocatalytic systems is critically reviewed to outline their design strategies, photocatalytic mechanisms, and environmental applications. These composites integrate bioderived polymers with metal oxide semiconductors, forming hybrid architectures that improve interfacial contact at the molecular level, enhance charge transfer efficiency, and impart higher structural flexibility. The polymer matrix not only provides mechanical adaptability and functional surface groups, but also serves as an environmentally friendly support that can modulate surface electronic states and influence the photoinduced electron-hole dynamics in the inorganic phase. By controlling the molecular interactions between the polymer chains and metal oxide surfaces, these hybrids can mitigate key limitations of conventional metal oxides, such as rapid electron-hole recombination and restricted visible-light absorption. This review first summarizes the fundamental electronic and structural properties of widely employed metal oxide semiconductors and highlights their intrinsic limitations in photocatalytic processes. It then examines the role of biopolymers from the perspective of molecular structure, charge transport pathways, and interfacial interaction mechanisms with the inorganic component. Various synthesis strategies-including sol-gel, hydrothermal, in situ nanoparticle generation, green synthesis, and surface functionalization-are discussed, with emphasis on their ability to tune the nanoscale morphology and interfacial chemistry of the hybrids. Applications of these biohybrid systems in dye degradation, pharmaceutical pollutant removal, heavy metal reduction, and antimicrobial photocatalysis are analyzed alongside mechanistic insights into charge separation efficiency and band alignment at the molecular interface. Furthermore, challenges related to long-term stability, reproducibility, scalability, and performance in real wastewater matrices are also addressed. Overall, this review provides a thorough discussion on the design principles, photocatalytic mechanism, and environmental applications of biobased hybrid semiconductors, while emphasizing future opportunities for the development of efficient and sustainable photocatalytic systems.