Catalytic Approaches of Biosynthesized Nanoparticles in the Construction of Organic Frameworks: A Green Chemistry Perspective

Incorporating biosynthesized nanoparticles (NPs) into metal–organic frameworks (MOFs) has been seen as a green and practical approach to designing sophisticated catalytic systems. Biosynthesised nanoparticles are more desirable than their chemical analogues due to their highest biocompatibility, nature-friendly process, and unique surface functionality, enhancing their catalytic activity. Furthermore, the capping agents with a biological background stabilize the nanoparticles and serve as active sites that favor selective reactions involved in the construction of frameworks. The chapter discusses catalysis processes of biosynthesized metal and metal oxide nanoparticles (Ag, Au, Cu, and ZnO NPs) for oxidation, C–C coupling, and condensation reactions that play critical roles during MOF, COF, and other POP syntheses have been emphasized. The chapter portrays silver NPs prepared using Azadirachta indica (neem) leaf extract for effective Knoevenagel condensation reaction to synthesize benzylidene-containing Covalent Organic Frameworks (COFs) at room temperature. Hierarchical MOF structures, such as PCN-222 nanorods epitaxially deposited on NU-1000 or UiO-66 octahedrons, are beneficial for biosynthesized NPs by incorporating meso-/macropores to overcome diffusion bottlenecks. Low-dimensional MOF heterostructures (1D/2D PCN-134 nanoplates) also leverage biosynthesized NPs to render active sites exposed and sequential catalysis feasible, as in enzyme-mimetic cascades are discussed. The green synthesis routes discussed here adhere to MOF sustainability goals through avoiding toxic reagents while allowing proper NP size regulation and dispersion. The chapter outlines that Acinetobacter calcoaceticus-derived Ag NPs entrapped in MIL-101(Cr) structures improved CO₂ reduction selectivity by 40% compared with chemically prepared analogs. Furthermore, anticancer drug-loaded biomineralized MOFs (such as doxorubicin@ZIF-8) utilized biosynthesized Fe₃O₄ NPs for magnetically targeted therapy, causing 80% tumour suppression in murine models. Besides, we address newer trends in bimodal functioning systems, where biosynthesized NPs serve as a catalyst and a component of structural hybrids, exhibiting polyfunctionality towards environmental remediation, fine chemicals synthesis, and energy storage applications. The chapter concludes by highlighting problems such as batch heterogeneity, scale-up limitations, and stability issues while hinting at directions like artificial intelligence-based green synthesis and hybridization with synthetic ligands. This dual approach is a paradigm shift towards sustainable, multifunctional catalytic platforms for next-generation material synthesis, offering a greener roadmap for next-generation chemical technologies.