Molecular Relaxation Processes in a MOF-5 structure revealed by broadband dielectric spectroscopy: signature of phenylene ring fluctuations
Stefan Frunza, Andreas Schnhals, Ligia Frunza, Paul Ganea, Hendrik Kosslick, Jrg Harloff, and Axel Schulz
J. Phys. Chem. B, September 16, 2010, 114 (40), pp 12840–12846

The molecular mobility of a MOF-5 metal−organic framework was investigated by broadband dielectric spectroscopy. Three relaxation processes were revealed. The temperature dependence of their relaxation rates follows an Arrhenius law. The process observed at lower temperatures is attributed to bending fluctuations of the edges of the cages involving the Zn−O clusters. The processes (“region II”) at higher temperatures were assigned to fluctuations of phenyl rings in agreement with the NMR data found by Gould et al. (J. Am. Chem. Soc. 2008, 130, 3246). The carboxylate groups might also be involved. The rotational fluctuations of the phenyl rings leading to the low frequency part of relaxation region II might be hindered either by some solvent molecules entrapped in the cages or by an interpenetrated structure and have a broad distribution of activation energies. The high frequency part of region II corresponds nearly to a Debye-like process: This is explained by a well-defined structure of empty pores.
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Removal of Reactive Blck 5 azo dye from aqueous solutions by catalytic oxidation using CuO/Al2O3 and NiO/Al2O3
Corina Bradu, Ligia Frunza, Nicoleta Mihalache, Sorin-Marius Avramescu, Marian Neat, Ion Udrea
Applied Catalysis B: Environmental, Numar: 96,Volume: 3-4pages 548-556

CuO/Al2O3 and NiO/Al2O3 catalysts prepared by incipient wetness impregnation were used for the oxidation of Reactive Black 5 (RB5) in aqueous solution. Removal of the dye was assessed by High Performance Liquid Chromatography (HPLC) and Total Organic Carbon (TOC) measurements and the generation of the hydroxyl radicals in the process was evaluated by chemiluminescence measurements. To put in evidence the interaction RB5 – catalyst and the surface species formed onto catalysts during the oxidation, Diffuse Reflectance Infrared Fourier Transform (DRIFT) analysis was performed. A different behavior of the two catalytic systems was revealed by the comparative analysis of the data obtained from the adsorption and oxidation tests. Only CuO/Al2O3 was effective in the RB5 degradation, NiO/Al2O3 acted as a simple adsorbent. In the presence of CuO/Al2O3, at H2O2 concentration of 40mM the azo dye was totally eliminated from both solution and catalyst surface after 4 h, with a mineralization degree higher than 90%. However, a strong inhibition of the catalytic oxidation of RB5 was observed in the presence of phosphate ions. In the conditions of hydrogen peroxide excess, the rate equation in the case of copper catalyst was simply expressed by a pseudo-first order equation and the model was found to fit well the data. The amount of copper leached from catalyst during the oxidation process was only 1.0–1.6% per cycle leading to the conclusion that the decrease of the dye mineralization with the number of cycles has to be explained mostly by the surface covering with the reaction products, at least to a certain extent

Chemiluminescence measurements for CuO/Al2O3, NiO/ Al2O3 and Al2O3