Improving the direct air capture capacity of grafted amines via thermal treatment.

This study investigates the effects of elevated temperature thermal treatments on the direct air capture of CO2 by aminosilane-grafted SBA-15 silica sorbents. Exposing samples to high temperatures (200-250 °C compared to 80-120 °C) in an inert environment resulted in improved CO2 capacity (5-21%) that was sustained over multiple adsorption/desorption cycles.

Functionalized cellulose nanofibril aerogels as cooperative acid-base organocatalysts for liquid flow reactions.

Cellulose nanomaterial aerogels are macroscopic porous solids with relatively high surface areas and are thus an interesting basis for renewable catalyst materials. Cross-linked acid-base bifunctional catalyst aerogels are produced here from TEMPO-oxidized cellulose nanofibrils (TOCNF) and demonstrated in both batch and flow catalysis. Recently established acid-base modification for catalysis is expanded upon for chemical or physical cross-linking with small molecules and polymers. Low density and relatively high surface area (up to 74 m2 g-1) aerogel catalysts are produced with a variety of processing approaches and then freeze-dried from water or tert-butyl alcohol/water mixtures. Finer pore structure and increased surface area are achieved with tert-butyl alcohol as co-solvent. Chemical cross-linking improved aerogel stability to solvents. Homogeneous and aerogel TOCNF catalysts are shown to be effective acid-base cooperative catalysts for aldol condensation reactions in batch reactions. Continuous flow reactions are performed with glass column reactors packed with aerogel catalysts that showed improved rates relative to batch experiments, while also demonstrating physical stability. Catalyst deactivation in flow reactions is observed and observations of deactivation support previously reported mechanisms of site poisoning by competitive chemisorption of reactants in analogous acid-base catalysts. This report is a key demonstration of cellulose nanofibril aerogels for catalysis in continuous liquid flow reactions.

Inter- and Intramolecular Cooperativity Effects in Alkanolamine-Based Acid-Base Heterogeneous Organocatalysts.

Intramolecular cooperativity in heterogeneous organocatalysts is investigated using alkanolamine-functionalized silica acid-base catalysts for the aldol condensation reaction of 4-nitrobenzaldehyde and acetone. Two series of catalysts, one with and one without silanol-capping, are synthesized with varied alkyl linker lengths (two to five) connecting secondary amine and terminal hydroxyl functionalities. The reactivity of these catalysts is assessed to determine the relative potential for intermolecular (silane amine-surface silanol) vs intramolecular (amine-hydroxyl within a single silane) cooperativity, the impact of inhibitory surface-silane interactions, and the role of alkyl linker length and flexibility. For the array of catalysts tested, those with longer linker lengths generally give increased catalytic activity, although the turnover frequency trends differ between catalysts with and without surface silanol capping. Catalysts with alkyl-substituted amines lacking a terminal hydroxyl demonstrate an adverse effect of chain length, where the larger alkyl substituent on the amine provides steric hindrance depressing catalytic activity, while giving additional evidence for improved rates afforded by intramolecular cooperativity in the alkanolamine materials. The silanol-capped alkanolamine catalyst with the longest alkyl linker is found to be the most active alkanolamine catalyst due to its hydrophobized surface, which removes hypothesized silanol-alkanolamine inhibitory interactions, with the sufficient length and flexibility of its amine-hydroxyl linker allowing for favorable conformations for cooperativity. This study demonstrates the feasibility of and important factors affecting intramolecular cooperative activity in acid-base heterogeneous organocatalysis.

Sequence of Hydrophobic and Hydrophilic Residues in Amphiphilic Polymer Coatings Affects Surface Structure and Marine Antifouling/Fouling Release Properties.

Amphiphilic polymers, specifically combinations of hydrophilic and hydrophobic residues, have been shown to be effective as antifouling materials against the algae Ulva linza and Navicula diatoms. Here we use the inherent sequence specificity of polypeptoids made by solid-phase synthesis to show that the sequence of hydrophilic (methoxy) and hydrophobic (fluorinated) moieties affects both antifouling and fouling release of U. linza. The platform used to test these sequences was a polystyrene-b-poly(ethylene oxide-co-allyl glycidyl ether) (PS-b-P(EO-co-AGE)) scaffold, where the polypeptoids are attached to the scaffold using thiol-ene click chemistry. The fluorinated moiety is very surface active and directs the surface composition of the polymer thin film. The position and number of fluorinated groups in the polypeptoid are shown to affect both the surface composition and antifouling properties of the film. Specifically, the position of the fluorinated units in the peptoid chain changes the surface chemistry and the antifouling behavior, while the number of fluorinated residues affects the fouling-release properties.