Hierarchical zeolites containing both micropores and mesopores are valuable catalysts for facilitating reactions of large molecules. Furan acylation by fatty acids is a promising reaction for valorizing biomass, and the self-pillared pentasil (SPP) zeolite was found to perform particularly well for this reaction. To better understand the distribution of molecules in hierarchical zeolites at the elevated temperature ($T=523$ K) and the elevated pressure ($p>1$ bar) associated with typical reaction conditions, unary and binary adsorption were predicted using Monte Carlo simulations in the isothermal–isobaric Gibbs ensemble. Adsorption of six species (furan, hexanoic acid, $n$-hexane, $n$-decane, $n$-tetradecane, and 3,6-diethyloctane) was investigated from vapor, liquid, and supercritical phases, and loadings into the micropores, onto the mesopore surface, and in the mesopore interior of SPP were obtained. As pressure increases, $n$-alkanes fill the micropores before loading the surface and then the interior of the mesopore, while furan and hexanoic acid adsorb strongly to the mesopore surface due to hydrogen bonding interactions with surface silanols. Hydrogen bonding interactions also draw hexanoic acid molecules in the micropore region toward the pore mouths, so their carboxylic acid group forms H-bonds with silanols, while the alkyl tails interact with the micropore walls. Mesopore condensation is observed for molecules below their critical point, and occurs when the Gibbs free energy of transfer into the mesopore interior and onto the mesopore surface converge. When hexanoic acid adsorption occurs in the presence of alkane solvents, then the selectivity and spatial distribution of hexanoic acid in the micropores and on the surface can be tuned by adjusting the fluid pressure and the alkane length and/or branching.

包含微孔和中孔的分层沸石是促进大分子反应的有价值的催化剂。脂肪酸对呋喃的酰化作用是使生物质增值的有前途的反应，并且发现自堆积的五碳硅（SPP）沸石在该反应中表现特别出色。为了更好地了解高温下分层沸石中分子的分布（$Ť=523$ K）和高压（$p>\mathrm{1个}$bar）与典型的反应条件有关，在等温-等压吉布斯系综中使用蒙特卡罗模拟预测了一元和二元吸附。吸附六种物质（呋喃，己酸，$ñ$正己烷 $ñ$-癸烷 $ñ$从气相，液相和超临界相研究了十六烷和3,6-二乙基辛烷，并获得了微孔，中孔表面和SPP中孔内部的负载量。随着压力的增加$ñ$-烷烃先填充微孔，然后再加载中孔表面，然后填充内部孔，而呋喃和己酸由于与表面硅烷醇的氢键相互作用而强烈吸附到中孔表面。氢键相互作用还将微孔区域中的己酸分子拉向孔口，因此它们的羧酸基团与硅烷醇形成H键，而烷基尾部与微孔壁相互作用。在低于其临界点的分子上观察到中孔凝结，并且当吉布斯自由能转移到中孔内部以及中孔表面汇聚时发生。当在烷烃溶剂存在下发生己酸吸附时，