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

Abstract

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.