Coordination of copper within a crystalline carbon nitride and its catalytic reduction of CO2.

Inherently disordered structures of carbon nitrides have hindered an atomic level tunability and understanding of their catalytic reactivity. Starting from a crystalline carbon nitride, poly(triazine imide) or PTI/LiCl, the coordination of copper cations to its intralayer N-triazine groups was investigated using molten salt reactions. The reaction of PTI/LiCl within CuCl or eutectic KCl/CuCl2 molten salt mixtures at 280 to 450 °C could be used to yield three partially disordered and ordered structures, wherein the Cu cations are found to coordinate within the intralayer cavities. Local structural differences and the copper content, i.e., whether full or partial occupancy of the intralayer cavity occurs, were found to be dependent on the reaction temperature and Cu-containing salt. Crystallites of Cu-coordinated PTI were also found to electrophoretically deposit from aqueous particle suspensions onto either graphite or FTO electrodes. As a result, electrocatalytic current densities for the reduction of CO2 and H2O reached as high as ∼10 to 50 mA cm-2, and remained stable for >2 days. Selectivity for the reduction of CO2 to CO vs. H2 increases for thinner crystals as well as for when two Cu cations coordinate within the intralayer cavities of PTI. Mechanistic calculations have also revealed the electrocatalytic activity for CO2 reduction requires a smaller thermodynamic driving force with two neighboring Cu atoms per cavity as compared to a single Cu atom. These results thus establish a useful synthetic pathway to metal-coordination in a crystalline carbon nitride and show great potential for mediating stable CO2 reduction at sizable current densities.

Toxin-Blocking Textiles: Rapid, Benign, Roll-to-Roll Production of Robust MOF-Fabric Composites for Organophosphate Separation and Hydrolysis.

Current approaches to create zirconium-based metal-organic framework (MOF) fabric composites for catalysis, water purification, wound healing, gas sorption, and other applications often rely on toxic solvents, long reaction/post processing times, and batch methods hindering process scalability. Here, a novel mechanism was reported for rapid UiO-66-NH2 synthesis in common low-boiling-point solvents (water, ethanol, and acetic acid) and revealed acid-base chemistry promoting full linker dissolution and vapor-based crystallization. The mechanism enabled scalable roll-to-roll production of mechanically resilient UiO-66-NH2 fabrics with superior chemical protective capability. Solvent choice and segregated spray delivery of organic linker and metal salt MOF precursor solutions allowed for rapid MOF nucleation on the fiber surface and decreased the energy and time needed for post-processing, producing an activated composite in less than 165 min, far outpacing conventional MOF-fabric synthesis approaches. The MOF-fabric hydrolyzed and blocked permeation of the chemical warfare agent soman, outperforming the protection-standard activated carbon cloth. This work presents both chemical insights into Zr-MOF powder and fabric composite formation by a rapid, industrially relevant approach and demonstrates its practicality and affordability for high-performing personal protective equipment.

Giant Lipid Vesicle Formation Using Vapor-Deposited Charged Porous Polymers.

In this study, we prepare giant lipid vesicles using vapor-deposited charged microporous poly(methacrylic acid- co-ethylene glycol diacrylate) polymer membranes with different morphologies and thicknesses. Our results suggest that vesicle formation is favored by thinner, more structured porous hydrogel substrates. Electrostatic interactions between the polymer and the lipid head groups affect vesicle yield and size distribution. Repulsive electrostatic interactions between the hydrogel and the lipid head groups promote vesicle formation; attractive electrostatic interactions suppress vesicle formation. Ionic strength and sugar concentration are also major parameters affecting the yield and size of giant vesicles. The presence of both ions and sugars in the hydration buffer results in increased vesicle yields. These results indicate that lipid-polymer interactions and osmotic effects in addition to the substrate morphology and surface charge are key factors affecting vesicle formation. Our data suggest that surface chemistry should be designed to tune electrostatic interactions with the lipid mixture of interest to promote vesicle formation. This vapor-deposited hydrogel fabrication technique offers tunability over the physicochemical properties of the hydrogel substrate for the production of giant vesicles with different sizes and compositions.