Computational Research Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
J Am Chem Soc. 2014 Apr 2;136(13):5006-22. doi: 10.1021/ja4123939. Epub 2014 Mar 24.
Porous polymer networks (PPNs) are a class of advanced porous materials that combine the advantages of cheap and stable polymers with the high surface areas and tunable chemistry of metal-organic frameworks. They are of particular interest for gas separation or storage applications, for instance, as methane adsorbents for a vehicular natural gas tank or other portable applications. PPNs are self-assembled from distinct building units; here, we utilize commercially available chemical fragments and two experimentally known synthetic routes to design in silico a large database of synthetically realistic PPN materials. All structures from our database of 18,000 materials have been relaxed with semiempirical electronic structure methods and characterized with Grand-canonical Monte Carlo simulations for methane uptake and deliverable (working) capacity. A number of novel structure-property relationships that govern methane storage performance were identified. The relationships are translated into experimental guidelines to realize the ideal PPN structure. We found that cooperative methane-methane attractions were present in all of the best-performing materials, highlighting the importance of guest interaction in the design of optimal materials for methane storage.
多孔聚合物网络（PPN）是一类先进的多孔材料，它结合了廉价稳定聚合物的优点和金属有机骨架的高比表面积和可调节化学性质。它们在气体分离或储存应用中特别感兴趣，例如，作为用于车载天然气罐或其他便携式应用的甲烷吸附剂。PPN 是由不同的构建单元自组装而成的；在这里，我们利用商业上可用的化学片段和两种实验已知的合成途径，设计了一个具有很大的、合成上合理的 PPN 材料数据库。来自我们的 18000 种材料数据库的所有结构都经过了半经验电子结构方法的松弛，并通过大正则蒙特卡罗模拟进行了甲烷吸收和可输送（工作）容量的特性研究。确定了许多控制甲烷储存性能的新的结构-性能关系。这些关系被转化为实验指南，以实现理想的 PPN 结构。我们发现，所有表现最好的材料中都存在协同的甲烷-甲烷吸引力，这突出了在设计用于甲烷储存的最佳材料时，客体相互作用的重要性。
