Covalent Organic Frameworks: Pore Design and Interface Engineering

, 2011, 2, 536). In this Account, we summarize the general concept of our approaches to various pore interfaces by emphasizing design principle, synthetic strategy, and distinct porous features and their impacts. We illustrate pore interface design by highlighting general strategies based on direct polymerization and pore surface engineering to construct different pore walls with a diversity of functional units. One distinct feature is that these functional groups are predesigned and synthetically controlled to achieve a predetermined component, position, and density, leading to a general way to install various specific pore wall interfaces to each pore. We showcase hierarchical pore interface architectures by elucidating the nature of interplays between interfaces and molecules and ions, ranging broadly from hydrogen bond to dipole-dipole/quadrupole interactions, electrostatic interaction, acid-base interaction, coordination, and electronic interactions. We scrutinize the unique properties and functions of adsorption and separation, catalysis, energy transformation and storage, and proton and metal ion transport by disclosing functional design schemes and interface-function correlations. We predict the fundamental key issues to be addressed and show future directions in designing artificial pores to target at ultimate functions. This chemistry on pore interface engineering opens a way to porous materials that have remained challenging in the predesign of both structure and function.