Catalyticpropertiesofthemetal-organicframeworkCr-MIL-101insolvent-freecycloadditionofCO2toepoxidestoproducecycliccarbonatesusingtetrabutylammoniumbromideasco-catalysthavebeenexploredundermildreactionconditions(8barCO2,25C).Styreneandpropylenecarbonateswereformedwithhighyields(95%and82%,respectively).CatalyticperformanceofCr-MIL-101wascomparedwithotherMOFs:Fe-MIL-101,Zn-MOF-5andHKUST-1.Thecatalyticpropertiesofdifferentquaternaryammoniumbromides,Cr-MIL-101aswellasPW12/Cr-MIL-101compositematerialhavebeenassessedinoxidativecarboxylationofstyreneinthepresenceofbothtert-butylhydroperoxideandH2O2asoxidantsat8100barCO2and2580Cwithselectivitytostyrenecarbonateupto44%at57%substrateconversion.