3D-monoclinic M–BTC MOF (M = Mn, Co, Ni) as highly efficient catalysts for chemical fixation of CO2 into cyclic carbonates

[(CH 3 ) 2 NH 2 ][M 3 (BTC)(HCOO) 4 (H 2 O)] . H 2 O (M–BTC, M   =   Mn, Ni, Co) were prepared under hydrothermal conditions and used as highly efficient catalysts for cycloaddition of CO 2 with epichlorohydrin (ECH). The microstructure and physicochemical properties of the compounds were determined by PXRD, FT-IR, XPS, N 2 -adsorption, TG–DSC, NH 3 –TPD and CO 2 –TPD. 98.01% conversion of ECH and 96.05% selectivity to chloropropene carbonate was obtained over the Mn–BTC under the optimized reaction conditions (105   °C, 3.0   MPa, 9   h, 1.5   wt.% of ECH). Besides, the recyclability result exhibited the Mn–BTC compound can be utilized as least three times with a slight reduction in its catalytic ability. In addition, cycloaddition of CO 2 with other epoxides and DFT calculation were also performed. The result exhibited the yield followed the order: ECH   >   1, 2-epoxybutane   >   propene oxide   >   Allyl glycidyl ether, which was mainly determined by the energy of reaction.