Role of cavities created by azobenzene-modified UiO-66 in bulky ionic liquid for high photoresponsive CO2 uptake behavior†
Abstract
Photoresponsive porous liquids (PLs) have been reported to capture CO2 which is controlled by light rather than the traditionally employed temperature and pressure. However, the change in CO2 uptake tailored by light is low (≤30%) over the reported photoresponsive PLs. Here, a new photoresponsive type III PL is prepared by dispersing a metal–organic framework (MOF, i.e. Azo-UiO-66 containing pendant azobenzene) in a polyethylene glycol-based dicationic bulky ionic liquid (IL). Intriguingly, 78% change in CO2 uptake upon UV and visible light irradiation is achieved by the PL with 5% Azo-UiO-66, which is much higher than those with pristine Azo-UiO-66 (38%) and neat IL (1%) as well as all reported photoresponsive PLs (≤30%). We demonstrate that, in addition to the intrinsic cavity in Azo-UiO-66, extrinsic cavity is created by the IL packing around the framework with the pendant azobenzene. Upon UV-light irradiation, the bending of the azobenzene groups conceals the active sites and causes dense packing of the IL encircling the MOF, which dissipates the extrinsic cavity and lowers CO2 adsorption. This is the first report on the generation of extrinsic cavity in PLs which is controllable by light irradiation, resulting in a different mechanism of light-regulated adsorption and a large change in CO2 uptake.
- This article is part of the themed collection: Journal of Materials Chemistry A HOT Papers