The Application Of Molecular Simulation In The Research On Covalent Organic Frameworks

Since the first covalent organic framework (COF) was synthesized by Yaghi group in 2005, the COF materials have drawn extensive attention because of its prospective and broad applications in gas adsorption, catalysis and photoelectric conversion. Meanwhile, as a promising technology of computational chemistry, the molecular simulation technology has been rapidly developed in recent years and is playing an important role in the field of material sciences and technology. We have attempted to apply molecular simulation technology to the investigations of COF materials in order to gain insights into the fundamental properties of COFs.In Chapter I, a brief introduction to the COF materials and molecular simulation technology was presented. The purpose and its significance of this research were also discussed.In Chapter II, we proposed the structural models of three imino-COFs based on the experimental PXRD data with the analysis of molecular simulation. The molecular simulation was adopted as a critical method in above-mentioned structural analysis. It successfully overcame the inherent limitation of using the PXRD method alone in the structural analysis of COFs.In Chapter III, a description of design of three new three-dimensional COF structures was given. These three-dimensional COF structures were then tested by Monte Carlo simulations. The structures were proven to be able to adsorb a large amount of methane (CH4) at 298 K and under the pressure ranging from 1 MPa to 10 MPa. Their thermodynamic stabilities were also verified by molecular dynamics simulation.In Chapter IV, a design of new COF containing Schiff base tautomeric fragments was presented. The absorption spectrum and energy barrier of the tautomer were calculated. Our result indicated that such COF with Schiff base structure is thermochromism.