Advanced synthesis and characterization of metal–organic frameworks for diverse applications

Abstract

Metal–organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) represent a remarkable class of porous crystalline materials, distinguished by their highly ordered structures, large surface areas, and chemical tunability. Their versatility makes them attractive for diverse applications, ranging from catalysis to environmental remediation. However, conventional solvothermal and hydrothermal syntheses often fall short in terms of precise microstructural control, largely due to limited real-time reaction monitoring and control. These drawbacks are particularly critical when the objective is not only to synthesize bulk powders but also to engineer functional coatings and composites for real-world applications. To address these challenges, this dissertation investigates non-conventional synthesis strategies for MOF- and ZIF-based coatings as well as their derived composites, with an emphasis on synthesis intensification, microstructural control, functionalization, and scalability, with the goal of expanding their applicability across environmental, energy, and health-related domains.

A solvent-free hot-press synthesis route was first developed for the fabrication of ZIF-8 nanostructures as photocatalytic coatings on protective masks. This approach eliminates the need for solvents while providing excellent control over crystallinity and adhesion. The resulting ZIF-8 films exhibited strong photocatalytic activity under UV irradiation, leading to the complete inactivation of bacterial pathogens and viral surrogates of COVID-19, demonstrating high potential for antimicrobial and health-protective applications. In the next stage, a microwave-assisted, template-directed growth approach was employed to construct hierarchically structured ZIF-67-based composites on carbon fiber substrates. The obtained materials displayed superhydrophobic and superoleophilic behavior, enabling highly efficient and selective oil–water separation, as well as excellent reusability and stability, thereby addressing key challenges in environmental remediation. Finally, a Ni-based MOF-74 composite was synthesized using a similar microwave-assisted, template-directed growth approach, followed by advanced laser-assisted post-treatment, enabling precise control over surface chemistry and hierarchical morphology. The resulting material exhibited outstanding electrocatalytic activity and durability toward the oxygen evolution reaction under alkaline conditions, underscoring the effectiveness of combining template-directed synthesis with post-synthetic laser modification for energyrelated applications.

Overall, this work establishes a coherent framework for non-conventional MOF synthesis and hierarchical composite design, demonstrating how synthesis intensification and targeted functionalization can drive material performance and broaden the practical impact of MOF-based technologies.