Theoretical Framework for the Design of Multi-Functional Metal-Organic Frameworks Derived from Nigerian Mineral Resources as Catalysts and Adsorbents

Metal-organic frameworks represent a class of porous coordination polymers with exceptional surface areas, tunable pore sizes, and multifunctional properties that position them as next-generation materials for catalysis, gas storage, drug delivery, and pollutant removal. The rational design of metal-organic frameworks using ligands and metal precursors derived from Nigerian mineral resources would constitute an original contribution to materials chemistry that leverages the country's natural resource endowment. This study developed a theoretical framework for the systematic design and computational screening of metal-organic frameworks synthesised from zinc and copper precursors available from Nigerian mineral deposits and carboxylate and azole bridging ligands synthesised from local petroleum feedstocks. Density functional theory calculations using periodic boundary conditions were performed to predict structural stability, pore geometry, surface energy, and adsorption properties for a library of sixty hypothetical frameworks. Thermodynamic stability was assessed through cohesive energy calculations. Pore structures were characterised computationally using Monte Carlo geometric analysis. Grand canonical Monte Carlo simulations were employed to model adsorption isotherms for carbon dioxide, methane, and methylene blue dye in the most promising candidate frameworks. Five candidate frameworks predicted to exhibit BET surface areas above 1,500 m2/g and methylene blue adsorption capacities exceeding 400 mg/g were identified and subjected to experimental validation through hydrothermal synthesis and characterisation. Experimental BET values matched computational predictions within 12 percent. The theoretical framework developed provides a rigorous, resource-efficient screening protocol for metal-organic framework discovery and represents an original theoretical contribution to porous materials science with direct application to Nigerian water treatment and carbon capture challenges.

Keywords: metal-organic frameworks, density functional theory, computational design, adsorption, Nigerian mineral resources