A highly stable dimethyl-functionalized Ce(iv)-based UiO-66 metal–organic framework material for gas sorption and redox catalysis. Issue 40 (29th September 2016) - Dalapati, Rana
Abstract : Gas sorption and the redox catalytic behaviour of a highly stable dimethyl-functionalized Ce(iv )-based UiO-66 framework material is presented. Abstract : The new, dimethyl-functionalized Ce(iv )-based UiO-66 (UiO = University of Oslo) metal–organic framework (MOF) material Ce-UiO-66-(CH3 )2 (1 ) was successfully synthesized under solvothermal conditions (100 °C, 15 min) by employing ammonium cerium(iv ) nitrate and the 2, 5-dimethyl-1, 4-benzenedicarboxylate (H2 BDC-(CH3 )2 ) ligand in a DMF/H2 O (DMF = N, N -dimethyl formamide) mixture. The phase purity of the as-synthesized and thermally activated form (1′ ) of the compound was confirmed by a combination of X-ray powder diffraction (XRPD) analysis, Fourier transform infrared (FT-IR) spectroscopy and thermogravimetric (TG) analysis. As verified by the thermogravimetric analysis, the compound is thermally stable up to 300 °C in air atmosphere. Based on the XRPD measurements, the material retains its crystallinity after treatment with water, methanol, acetic acid and 1 M HCl. As confirmed by the gas sorption experiments, the compound shows significant microporosity towards N2 (BET surface area = 845 m 2 g −1 ) and CO2 (adsorption capacity = 34 cm 3 g −1 at 0 °C and 1 bar). The catalytic activity of1′ has been studied in the oxidation of styrene and cyclohexene using tert -butylhydroperoxide (TBHP) as the terminal oxidant. The catalyst is reusable for four cycles with no significant drop in its activity which is further confirmed by a hot filtration experiment.