Investigating the Physical Adsorption of DCPD/Furfural and H Adsorption-Dissociation Behaviors in RE-MOFs.

Metal-organic frameworks (MOFs) have emerged as promising catalysts in the hydrogenation of bicyclopentadiene (DCPD) and furfural. The physical adsorption behaviors of substrate molecules and H within the pore structures of MOFs significantly influence the efficacy of subsequent catalytic reactions. This study employs molecular dynamics (MD) simulations to identify the optimal temperature and pressure conditions for the adsorption of DCPD and H, as well as furfural and H, within rare-earth-element-based MOFs (RE-MOFs). By analyzing the physical adsorption characteristics of 1538 RE-MOFs, we investigate the correlation between pore structures and adsorption capabilities. This exploration has led to the identification of 10 RE-MOF structures that demonstrate superior physical adsorption performance for both DCPD and furfural. Following this initial evaluation, density functional theory (DFT) calculations were conducted to determine the chemisorption energies of H molecules on these 10 selected RE-MOF structures. Notably, the structure identified as "JALLEQ_clean" exhibited the most optimal overall adsorption performance. This study elucidates the quantitative relationship between the pore structure of RE-MOFs and their physical adsorption performance, clarifying the influence of porosity parameters on adsorption capacity and highlighting the advantages of cluster-type structures in mass transfer and adsorption. The findings provide theoretical guidance for developing high-performance RE-MOF catalysts and offer new insights for the rational design of MOF-based catalytic materials.