Design principles of advanced porous materials for efficient CO2 capture and electrochemical reduction

Abstract

This thesis presents a joint comprehensive theoretical and computational investigation into the rational design of porous materials for CCUS, with a particular focus on MOFs and COFs. Using a combination of non-periodic DFT, hybrid periodic DFT, and post-Hartree-Fock (HF) calculations, the thesis systematically has explored the adsorption and catalytic behavior of functionalized porous materials toward efficient CO2 capture and electrochemical reduction. The overall objective of the thesis was to study the CO2 adsorption strength, electronic properties, catalytic activity, and product selectivity in MOF and COF-based systems. Overall, this thesis presents a strong theoretical understanding connecting adsorption behavior, electronic structure, and catalytic performance in porous MOFs and COFs. By integrating molecular-level adsorption studies with periodic catalytic investigations, the work provides fundamental insights into the design principles required for efficient CO2 capture and electrochemical conversion. The systematic exploration of linker effects, metal-center activity, and structure engineering advances the understanding of how porous crystalline materials can be tailored for specific CCUS applications. The present thesis provides a joint theoretical and computational foundation for the rational design of porous MOFs and COFs for CO2 capture and electrochemical conversion. Although significant insights have been obtained regarding adsorption energies, electronic properties, and catalytic pathways, several promising directions remain open for future exploration.