In silico Design of Three-Dimensional Porous Covalent Organic Frameworks via Known Synthesis Routes and Commercially Available Species

R. L. Martin, C. M. Simon, B. Medasani, D. K. Britt, B. Smit, and M. Haranczyk, In silico Design of Three-Dimensional Porous Covalent Organic Frameworks via Known Synthesis Routes and Commercially Available Species J. Phys. Chem. C., 118 (41), 23790–23802 (2014)   http://dx.doi.org/10.1021/jp507152j

jp-2014-07152j_0008

Abstract Covalent organic frameworks (COFs) are a class of advanced nano-porous polymeric materials which combine the crystallinity of metal-organic 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 semi-empirical 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 4,147 structures (based on 620 unique non-interpenetrated 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.

© Berend Smit 2019