Niu Muye, Xi Zuoshuai, He Chenhui, Ding Wenting, Cheng Shanshan, Zhang Juntao, Gao Hongyi
Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China.
Shunde Innovation School, University of Science and Technology Beijing, Foshan 528399, China.
Molecules. 2025 Apr 28;30(9):1954. doi: 10.3390/molecules30091954.
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.
金属有机框架材料（MOFs）已成为双环戊二烯（DCPD）和糠醛加氢反应中颇具前景的催化剂。底物分子和氢气在MOFs孔结构内的物理吸附行为显著影响后续催化反应的效果。本研究采用分子动力学（MD）模拟来确定基于稀土元素的MOFs（RE-MOFs）中DCPD与氢气以及糠醛与氢气吸附的最佳温度和压力条件。通过分析1538种RE-MOFs的物理吸附特性，我们研究了孔结构与吸附能力之间的相关性。此次探索已确定了10种RE-MOF结构，它们对DCPD和糠醛均表现出卓越的物理吸附性能。在这一初步评估之后，进行了密度泛函理论（DFT）计算，以确定氢分子在这10种选定的RE-MOF结构上的化学吸附能。值得注意的是，被确定为“JALLEQ_clean”的结构展现出最为理想的整体吸附性能。本研究阐明了RE-MOFs孔结构与其物理吸附性能之间的定量关系，明确了孔隙率参数对吸附容量的影响，并突出了簇型结构在传质和吸附方面的优势。这些发现为开发高性能RE-MOF催化剂提供了理论指导，并为基于MOF的催化材料的合理设计提供了新的见解。
