Metal Oxide-Derived MOF-74 Polymer Composites through Pickering Emulsion-Templating: Interfacial Recrystallization, Hierarchical Architectures, and CO2 Capture Performances.

Currently, metal-organic framework (MOF)-polymer composites are attracting great interest as a step forward in making MOFs a useful material for industrially relevant applications. However, most of the research is engaged with finding promising MOF/polymer pairs and less with the synthetic methods by which these materials are then combined, albeit hybridization has a significant impact on the properties of the new composite macrostructure. Thus, the focus of this work is on the innovative hybridization of MOFs and polymerized high internal phase emulsions (polyHIPEs), two classes of materials that exhibit porosity at different length scales. The main thrust is the in situ secondary recrystallization, i.e., growth of MOFs from metal oxides previously fixed in polyHIPEs by the Pickering HIPE-templating, and further structure-function study of composites through the CO2 capture behavior. The combination of Pickering HIPE polymerization and secondary recrystallization at the metal oxide-polymer interface proved advantageous, as MOF-74 isostructures based on different metal cations (M2+ = Mg, Co, or Zn) could be successfully shaped in the polyHIPEs' macropores without affecting the properties of the individual components. The successful hybridization resulted in highly porous, co-continuous MOF-74-polyHIPE composite monoliths forming an architectural hierarchy with pronounced macro-microporosity, in which the MOF microporosity is almost completely accessible for gases, i.e., about 87% of the micropores, and the monoliths exhibit excellent mechanical stability. The well-structured porous architecture of the composites showed superior CO2 capture performance compared to the parent MOF-74 powders. Both adsorption and desorption kinetics are significantly faster for composites. Regeneration by temperature swing adsorption recovers about 88% of the total adsorption capacity of the composite, while it is lower for the parent MOF-74 powders (about 75%). Finally, the composites exhibit about 30% improvement in CO2 uptake under working conditions compared to the parent MOF-74 powders, and some of the composites are able to retain 99% of the original adsorption capacity after five adsorption/desorption cycles.

Functional macroporous amphoteric polyelectrolyte monoliths with tunable structures and properties through emulsion-templated synthesis.

HYPOTHESIS: Macroporous polyampholyte hydrogels, simultaneously bearing both the anionic and cationic groups, demonstrate immense promise over the one-sign charged polyelectrolytes, owing to a unique phenomenon known as the ˝anti-polyelectrolyte˝ effect. Thus, they are extremely promising materials, since they remain solvated and functional even in harsh conditions. Furthermore, macroporous morphology significantly enhances polyampholyte response to external stimuli, since it accelerates the solvent transport through the hydrogel. EXPERIMENTS: A new templated-synthesis through "HIPE mixtures" is reported, where the two pre-formed high internal phase emulsions (HIPE) containing the oppositely charged monomers (2-acrylamido-2-methyl-1-propanesulfonic acid and (3-acrylamidopropyl)trimethylammonium chloride) were combined in the same mould, which after polymerization result in the formation of macroporous monoliths of different structures. The resulting frameworks were either copolymer or dual homopolymers in the form of bilayered or mixed porous structures. FINDINGS: The co- and mixed-amphoteric polyelectrolytes exhibit 'anti-polyelectrolyte' behaviour typical of polyampholytes, while the bilayered-structure behaves like a typical polyelectrolyte. Complete and simultaneous removal of both dyes from a dye mixture was observed for the bilayered- and mixed-amphoteric polyelectrolyte, while copoly-ampholyte showed only partial dye adsorption. These results clearly reveal the benefits of a mutual combination of the HIPE-templated structure and the oppositely charged amphoteric nature in one-piece material as a promising avenue toward advanced materials.