The Influence of Disorder in the Synthesis, Characterization and Applications of a Modifiable Two-Dimensional Covalent Organic Framework.

Two-dimensional covalent organic frameworks (2D-COFs) have been of increasing interest in the past decade due to their porous structures that ideally can be highly ordered. One of the most common routes to these polymers relies on Schiff-base chemistry, i.e., the condensation reaction between a carbonyl and an amine. In this report, we elaborate on the condensation of 3,6-dibromobenzene-1,2,4,5-tetraamine with hexaketocyclohexane (HKH) and the subsequent carbonylation of the resulting COF, along with the possibility that the condensation reaction on HKH can result in a trans configuration resulting in the formation of a disordered 2D-COF. This strategy enables modification of COFs via bromine substitution reactions to place functional groups within the pores of the materials. Ion-sieving measurements using membranes from this COF, reaction of small molecules with unreacted keto groups along with modeling studies indicate disorder in the COF polymerization process. We also present a Monte Carlo simulation that demonstrates the influence of even small amounts of disorder upon both the 2D and 3D structure of the resulting COF.

A Highly Ordered Nanoporous, Two-Dimensional Covalent Organic Framework with Modifiable Pores, and Its Application in Water Purification and Ion Sieving.

The preparation of membranes with high selectivity based on specific chemical properties such as size and charge would impact the efficiency of the world's energy supply, the production of clean water, and many other separation technologies. We report a flexible synthetic protocol for preparing highly ordered two-dimensional nanoporous polymeric materials (termed covalent organic frameworks or COFs) that allow for placing virtually any function group within the nanopores. We demonstrate that membranes, fabricated with this new family of materials with carboxylated pore walls, are very water permeable, as well as highly charged and size selective.

Elucidation of Titanium Dioxide Nucleation and Growth on a Polydopamine-Modified Nanoporous Polyvinylidene Fluoride Substrate via Low-Temperature Atomic Layer Deposition.

Interfaces combining polydopamine (PDA) and nanoparticles have been widely utilized for fabricating hybrid colloidal particles, thin films, and membranes for applications spanning biosensing, drug delivery, heavy metal detection, antifouling membranes, and lithium ion batteries. However, fundamental understanding of the interaction between PDA and nanoparticles is still limited, especially the impact of PDA on nanoparticle nucleation and growth. In this work, PDA is used to generate functional bonding sites for depositing titanium dioxide (TiO2) via atomic layer deposition (ALD) onto a nanoporous polymer substrate for a range of ALD cycles (<100). The resulting hybrid membranes are systematically characterized using water contact angle, scanning electron microscopy, atomic force microscopy, nitrogen adsorption and desorption, and X-ray photoelectron spectroscopy (XPS). An intriguing nonlinear relationship was observed between the number of ALD cycles and changes in surface properties (water contact angle and surface roughness). Together with XPS study, those changes in surface properties were exploited to probe the nanoparticle nucleation and growth process on complex PDA-coated porous polymer substrates. Molecular level understanding of inorganic and polymer material interfaces will shed light on fine-tuning nanoparticle-modified polymeric membrane materials.