In Silico Design of Three-Dimensional Porous Covalent Organic Frameworks via Known Synthesis Routes and Commercially Available Species
In Silico Design of Three-Dimensional Porous Covalent Organic Frameworks via Known Synthesis Routes and Commercially Available Species
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DOI：
10.1021/jp507152j
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发表时间：
2014-10-16
影响因子：
3.7
通讯作者：
Haranczyk, Maciej
中科院分区：
文献类型：
--
作者：
Martin, Richard L.;Simon, Cory M.;Haranczyk, Maciej
共价有机骨架（COFs）是一类先进的纳米多孔聚合物材料，它将金属有机骨架（MOFs）的结晶性与多孔聚合物网络（PPN）的稳定性和潜在的低成本有机化学结合在一起，具有联合收割机的优点。像其他先进的多孔材料一样，COF可以被设计成满足各种应用的需求，从能源到安全，再到人类健康。在这项工作中，我们构建了一个数据库的假设三维，晶体COFs。在构建该文库时，我们仅使用已建立的合成路线、先前利用的四面体构建单元和市售的桥接接头分子来产生新型COF。这确保了在我们的数据库中合成所有材料时没有已知的化学障碍。我们通过半经验电子结构计算放松了数据库中的所有材料。此外，对于那些允许相互渗透的结构，我们设计了基本结构的相互渗透版本。然后，我们表征了这些结构中的每一个的孔隙度。最后一组4147个结构（基于620个独特的非互穿结构）和它们的计算属性是公开的，可以筛选，以确定有前途的材料，用于各种各样的应用。在这里，我们评估的适用性，我们的COFs车辆甲烷存储进行分子模拟预测的平衡甲烷吸收。
Covalent organic frameworks (COFs) are a class of advanced nanoporous polymeric materials which combine the crystallinity of metalorganic frameworks (MOFs) with the stability and potentially low-cost organic chemistry of porous polymer networks (PPNs). Like other advanced porous materials, COFs can potentially be designed to meet the needs of a variety of applications, from energy, to security, to human health. In this work, we construct in silico a database of hypothetical three-dimensional, crystalline COFs. In constructing this library we generate novel COFs using only established synthetic routes, previously utilized tetrahedral building units, and commercially available bridging linker molecules. This ensures that there are no known chemical barriers to synthesizing all materials in our database. We relaxed all materials in our database through semiempirical electronic structure calculations. In addition, for those structures that allow interpenetration, we designed interpenetrated versions of the basic structure. Then, we characterized the porosity of each of these structures. The final set of 4147 structures (based on 620 unique noninterpenetrated structures) and their computed properties are publicly available and can be screened to identify promising materials for a wide variety of applications. Here, we assess the suitability of our COFs for vehicular methane storage by performing molecular simulations to predict the equilibrium methane uptake.