Enhanced Photocatalytic Activity of {110}-Faceted TiO2 Rutile Nanorods in the Photodegradation of Hazardous Pharmaceuticals.

Rutile TiO2 with highly active facets has attracted much attention owing to its enhanced activity during the photocatalytic degradation of pollutants such as pharmaceuticals in wastewater. However, it is difficult to obtain by controlling the synthetic conditions. This paper reports a simple hydrothermal synthesis of rutile TiO2 nanorods with highly exposed {110} facets. The obtained rutile was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and Raman spectroscopy. The main contribution to the photocatalytic activity comes from rutile nanorods with highly dominant active {110} facets, which were studied in the photodegradation of reactive cinnamic acid and more recalcitrant ibuprofen. The contribution of active species was also investigated. The present work further confirmed the hydrothermal synthesis route for controlling the preparation of highly crystalline and active rutile nanocrystals.

Room-temperature synthesis of zinc oxide nanoparticles in different media and their application in cyanide photodegradation.

Cyanide is an extreme hazard and extensively found in the wastes of refinery, coke plant, and metal plating industries. A simple, fast, cost-effective, room-temperature wet chemical route, based on cyclohexylamine, for synthesizing zinc oxide nanoparticles in aqueous and enthanolic media was established and tested for the photodegradation of cyanide ions. Particles of polyhedra morphology were obtained for zinc oxide, prepared in ethanol (ZnOE), while spherical and some chunky particles were observed for zinc oxide, prepared in water (ZnOW). The morphology was crucial in enhancing the cyanide ion photocatalytic degradation efficiency of ZnOE by a factor of 1.5 in comparison to the efficiency of ZnOW at an equivalent concentration of 0.02 wt.% ZnO. Increasing the concentration wt.% of ZnOE from 0.01 to 0.09 led to an increase in the photocatalytic degradation efficiency from 85% to almost 100% after 180 min and a doubling of the first-order rate constant (k).

Molecular relaxation processes in a MOF-5 structure revealed by broadband dielectric spectroscopy: signature of phenylene ring fluctuations.

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.

Composites containing confined n-octyl-cyanobiphenyl: monomer and dimer species in the surface layer by in situ FTIR spectroscopy.

Confinement of 4-n-octyl-4'-cyanobiphenyl (8CB) to nanoporous molecular sieves with hexagonal structure of cylindrical pores (4.6nm diameter) is studied. Thermogravimetric investigations have indicated that the pores are completely filled. Several surface species inside the pores and onto the external surface of the grains were demonstrated by differential thermal analysis and by in situ infrared spectroscopy. Arguments are given that bulk-like monomer and dimer species along with hydrogen bonded ones might coexist in the so-called surface layer, but their population varies drastically as function of the temperature. In addition, chemical changes of the confined liquid crystal are quite possible inside these nanopores, at temperatures lower than for the bulk.

Phase behavior and molecular mobility of n-octylcyanobiphenyl confined to molecular sieves: dependence on the pore size.

The molecular dynamics of 4-n-octyl-4'-cyanobiphenyl (8CB) confined inside the pores of a series of AlMCM-41 samples with the same structure, constant composition (SiAl=14.7) but different pore sizes (diameter between 2.3 and 4.6 nm) was investigated by broadband dielectric spectroscopy (10(-2)-10(9) Hz) in a large temperature interval. Two relaxation processes are observed: one has a bulklike behavior and is assigned to the 8CB in the pore center. The relaxation time of the second relaxation process is essentially slower than that of the former one and this process is related to the dynamics of molecules in a surface layer with a paranematic order. Both relaxation processes are specifically influenced by the interaction of the molecules with the surface and by the confinement. Above the clearing temperature the temperature dependence of the relaxation rate of the bulklike process obeys the Vogel-Fulcher-Tammann (VFT) law. The Vogel temperature increases with decreasing pore size. This is explained by increasing influence of paranematic potential of the surface layer with decreasing pore size. The temperature dependence of the relaxation rate of the surface layer follows also the VFT formula and the Vogel temperature decreases with decreasing pore size. This temperature dependence is controlled by both the interaction of the 8CB molecules with the surface via hydrogen bonding and by spatial confinement effects. To discriminate between both effects the data for the surface layer of 8CB confined to the molecular sieves are compared with results concerning 8CB adsorbed as a quasimonolayer on the surface of silica spheres of aerosil. On this basis a confinement parameter is defined and discussed.

Rotational fluctuations of water inside the nanopores of SBA-type molecular sieves.

The rotational molecular dynamics of water confined to nanoporous molecular sieves of a regular hexagonal (SBA-15) and of a foamlike pore structure was studied by dielectric spectroscopy in the frequency range from 10(-2) to 10(9) Hz and in a broad temperature interval. Two relaxation processes were observed: the process at lower frequencies is related to water molecules forming a layer, which is strongly adsorbed at the pore surface, whereas the relaxation process at higher frequencies is assigned to fluctuations of water molecules situated close to the center of the pore. The relaxation times of the low-frequency process for both materials and of the high-frequency process for the SBA-15 material have an unusual saddlelike temperature dependence, reported here for the first time. To describe this temperature dependence, a model developed for water confined to nanoporous glasses by Ryabov et al. [J. Phys. Chem. B 2001, 105, 1845] was applied, which considers two competing effects. The characteristic features of these two competing processes were compared with those reported for other porous systems.