Bonakala Satyanarayana, Balasubramanian Sundaram
Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research , Bangalore 560 064, India.
J Phys Chem B. 2016 Jan 28;120(3):557-65. doi: 10.1021/acs.jpcb.5b08842. Epub 2016 Jan 14.
Structural models and physical properties of several amorphous microporous polymers (AMPs) have been investigated using molecular dynamics simulations in an all-atom framework. The modeled structures of AMPs are quantitatively consistent with experimental observations. A linear relationship between the accessible surface area (ASA) and mass density of AMPs has been established. In the AMP network constituted by planar nodes, near-neighbor nodes are oriented parallel to each other. The microporous structural models are further validated by the calculation of CO2 and N2 adsorption isotherms at 298 and 77 K, respectively, obtained through Grand Canonical Monte Carlo (GCMC) simulations. The isotherms and isosteric heat of adsorption computed within a force field approach are able to well reproduce the experimental results. The nature of interactions between the functional groups of the AMPs framework and CO2 have been identified. An excellent CO2 uptake with high heat of adsorption has been observed in AMPs containing nitrogen-rich building blocks.
在全原子框架下，利用分子动力学模拟研究了几种无定形微孔聚合物（AMPs）的结构模型和物理性质。AMPs的模拟结构与实验观测结果在定量上是一致的。已建立了AMPs的可及表面积（ASA）与质量密度之间的线性关系。在由平面节点构成的AMP网络中，近邻节点相互平行排列。通过巨正则蒙特卡罗（GCMC）模拟分别计算了298K和77K下CO2和N2的吸附等温线，进一步验证了微孔结构模型。在力场方法中计算得到的等温线和吸附等量热能够很好地重现实验结果。已确定了AMPs骨架官能团与CO2之间相互作用的性质。在含有富氮结构单元的AMPs中观察到了具有高吸附热的优异CO2吸收性能。
