Boosted mass transfer and water tolerance in CO2 cycloaddition via hierarchically porous PVMDMS@PVP aerogel containing in-situ grown UiO-66-NH2

A covalently co-networked poly(vinylmethyldimethoxysilane)/polyvinylpyrrolidone (PVMDMS@PVP) aerogel scaffold enables in-situ growth of UiO-66-NH2 and grafting of 1-methylacetamido-3-methylimidazolium bromide ([MAmim]Br), forming a monolithic catalyst for integrated carbon dioxide (CO2) capture and cycloaddition reaction. Tuning PVP content (5–20 wt %) during sol–gel synthesis yields a hierarchically porous network (> 1,000 m2·g–1) that resists collapse under solvothermal conditions. Solvothermal crystallization within the network produces uniformly dispersed UiO-66-NH2 (~ 34 wt %) without pore blockage, and ionic liqud (IL) grafting introduces dual sites for CO2 adsorption and epoxide activation. The composite achieves 2.8 mmol g–1 CO2 uptake at 25 °C and promotes solvent- and co-catalyst-free cycloaddition of allyl glycidyl ether (AGE) at 120 °C, 0.6 MPa CO2 to > 99% conversion and selectivity with 0.151 mol % catalyst loading. Ten consecutive adsorption–desorption and reaction cycles retain > 97% of activity and structural integrity. An apparent activation energy of 37.5 kJ mol–1 (vs. 47.8 kJ·mol–1 for UiO-66-NH2-IL) highlights accelerated kinetics. Exceptional water tolerance and multi-cycle stability underscore its potential as a scalable platform for practical CO2 valorization.