Institut Charles Gerhardt Montpellier, UMR CNRS 5253, UM2, ENSCM, Place E. Bataillon, 34095 Montpellier cedex 05, France.
Phys Chem Chem Phys. 2010 Jun 28;12(24):6428-37. doi: 10.1039/c001173h. Epub 2010 May 7.
The adsorption of short linear alkanes has been explored in the highly flexible MIL-53(Cr) porous metal-organic framework by means of molecular simulations based on configurational bias grand canonical Monte Carlo. The unusual shape of the adsorption isotherms with the existence of steps has been successfully modelled by creating a (narrow pore, large pore) phase mixture domain, the composition of which varies with pressure. A further step consisted of combining our computational approach with several experimental tools including microcalorimetry, gravimetry and in situ X-ray diffraction, to fully characterize the adsorption behaviour of the isostructural MIL-47(V) rigid MOF, i.e. the preferential arrangement of each type of alkane inside the pores and the resulting interaction energy. Finally, relationships are established between the adsorption enthalpies and both alkyl chain length and polarisability of the alkanes that can be further utilised to predict the energetics of the adsorption process for longer alkane chains.
采用基于构象偏倚正则系综蒙特卡罗法的分子模拟研究了短链线性烷烃在高柔性 MIL-53(Cr) 多孔金属有机骨架中的吸附情况。通过创建一个（窄孔、大孔）相混合域，成功地模拟了具有台阶的不寻常形状的吸附等温线，该混合域的组成随压力而变化。进一步的步骤是将我们的计算方法与包括微热量测定法、重量分析法和原位 X 射线衍射法在内的几种实验工具相结合，以充分表征同构 MIL-47(V) 刚性 MOF 的吸附行为，即每种类型的烷烃在孔内的优先排列方式和由此产生的相互作用能。最后，建立了吸附焓与烷烃的烷基链长度和极化率之间的关系，可进一步用于预测更长烷烃链的吸附过程的能量学。
