High internal phase emulsion (HIPE) templating offers an efficient approach to prepare 3D hierarchical porous metal-organic framework (MOF)-based monoliths. However, conventional poly-Pickering HIPEs synthesized from MOF-stabilized HIPEs have low permeability due to closed-cell structures, thus limiting their applications. Herein, interconnected porous MOF monoliths, prepared by adding a small amount of polyvinyl alcohol (PVA) as co-stabilizer into UiO-66 stabilized Pickering HIPE templates are reported. The morphology of the porous monoliths was studied by scanning electron microscopy (SEM). The pore size could be well controlled by varying the PVA concentration. A unique morphology, formed by an ice template, was clearly seen on the cell wall. The pores were thus interconnected. The mass transfer performance of the monoliths having different cell structures was investigated by CO adsorption. The interconnected porous structure significantly accelerated the CO adsorption process, as well as enhancing the saturated adsorption capacity.
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