Gabriela Dyrda

TiO2-based Photocatalysts Impregnated with Metallo-Porphyrins Employed for Degradation of 4-Nitrophenol in Aqueous Solutions: Role of Metal and Macrocycle

Photodegradation of organic compounds in water solutions by means of economically advantageous and environment-friendly processes is a topic of growing interest. In recent years a great attention has been devoted to TiO2-based photocatalysts for the oxidative degradation of various organic pollutants. In this context, we have prepared new photo-catalytic polycrystalline TiO2 systems impregnated with sensitizers, i.e., copper, iron or manganese porphyrins, and investigated their photoactivity for 4-nitrophenol oxidation compared with that of bare TiO2. A significant improvement of the photoreactivity was observed in the case of TiO2 impregnated with copper porphyrin, while only a slight beneficial effect was observed in the case of iron porphyrin. In contrast, the presence of manganese porphyrin appeared to be detrimental.

Novel Lipophilic Lanthanide Bis-Phthalocyanines Functionalized by Pentadecylphenoxy Groups: Synthesis, Characterization and UV-Photostability

Novel sandwich-type phthalocyanines containing a rare earth metal core (Pr, Nd, Eu–Lu) and macrocycles peripherally substituted by pentadecylphenoxy groups were synthesized using a cardanol-based phthalonitrile precursor and the respective lanthanide acetate. Additionally, the metal free-base analog compound was studied for comparison. The purified reaction products were all found to be thick and viscous substances at room temperature, showing liquid crystalline behavior with a distinct increase in fluidity at ca. 40 °C. The complexes are readily soluble in chloroalkyl solvents and dissolve fairly well in DMF with some tendency to form aggregates. Besides they are strongly hydrophobic and reveal a peculiar affinity for lipophilic media. The compounds have been characterized by UV-Vis (absorption and emission), FTIR, MS and DSC methods. Photochemical activity in the liquid phase (dimethylformamide, dichloromethane, mineral oil) and the degree of photodegradation demonstrated under constant UV-irradiation (λ = 352 nm) have been analyzed and discussed in terms of photostability.

Structural and Molecular Characterization of meso-Substituted Zinc Porphyrins: A DFT Supported Study

Structural parameters of a range of over 100 meso-substituted zinc porphyrins were reviewed and compared to show how far the nature of the functional group may affect the interatomic distances and bond angles within the porphyrin core. It was proved that even despite evident deformations of the molecular structure, involving twisting of the porphyrins central plane, the coupled π-bonding system remains flexible and stable. DFT calculations were applied to a number of selected porphyrins representative for the reviewed compounds to emphasize the relevance of theoretical methods in structural investigations of complex macrocyclic molecular systems. Experimental and DFT-simulated IR spectral data were reported and analyzed in context of the individual molecular features introduced by the meso substituents into the porphyrin moiety base. Raw experimental spectral data, including 1H- and 13C-NMR, UV-Vis, FTIR, XRD, and other relevant physicochemical details have been provided for a specially chosen reference zinc porphyrin functionalized by tert-butylphenyl groups.

Effect of air-absorbed oxygen and moisture on the chemical stability of photoexcited Mg, Zn and Eu phthalocyanines in dimethylformamide

Absorption of oxygen and moisture from air by MPc-DMF systems was studied and related to the molecular stability demonstrated by phthalocyanine complexes (unsubstituted MPcs: MgPc, ZnPc and EuPc2; Pc = phthalocyanine ligand, C32H16N8) subjected to UV irradiation. A lower stability of air-exposed dimethylformamide solutions is observed and is due to a specific affinity for molecular oxygen revealed by the Pc macrocycle. SEM results proved oxygen molecules fixed to the phthalocyanine solids by forces strong enough to sustain desorption under vacuum. Absorption curves determined for MPc-DMF systems also indicate oxygen accommodated by the phthalocyanine moiety. This explains the predominantly oxygen-mediated photolysis, as well as the very short fluorescence lifetimes of metal phthalocyanines. The effect of air-absorbed moisture on the photostability is much less pronounced and practically insignificant for concentrations of H2O lower than 1%. An apparent stabilizing effect of water was observed and elucidated basing on kinetic considerations. The degradation rate of the photoexcited phthalocyanine moiety in air-exposed solutions depends on individual chemical properties and the molecular structure of the complex. EuPc2 proved very stable whereas the photostability of ZnPc and MgPc gradually decreased in the course of time.

meso-Aryl-substituted free-base porphyrins: formation, structure and photostability of diprotonated species

Susceptibility to interact with trifluoroacetic acid (TFA) of selected free-base porphyrins, including a novel lipophilic 3-n-pentadecyl(phenoxy)-ethoxy-phenyl-substituted porphyrin, and photostability of their diprotonated compounds was explored in benzene and N,N-dimethylformamide (DMF). Results have been discussed in terms of the commonly applied pKa-based procedure and confronted with a simple approach derived from experimentally-determined correlations reflecting the porphyrins affinity for TFA. Density functional theory (DFT) has proved the porphyrin moiety creates stable diprotonated species involving two TFA molecules, in which the fluorine atoms effectively contribute to the overall interaction of the acid with the porphyrin macrocycle. The relevance of the meso-substituent and ambient medium to the reactivity and photostability of diverse porphyrin derivatives was emphasized and referred to structural features of the investigated diprotonated porphyrins.

Activity of phthalocyanine-sensitized TiO2-anatase in photooxidation of sulfite ions

Abstract Hybrid catalysts based on the TiO2 matrix impregnated with Nd, Eu and Yb diphthalocyanines proved effective in oxidation of sulfite ions under irradiation with light from the UV-visible range. Micro- and nano-crystalline anatase powders were used in preparation of the photocatalysts, which were applied in the form of a suspension in the water phase. The reaction yield was found to depend on the phthalocyanine sensitizer used and the conditions of TiO2 impregnation. The best results were obtained when micro-anatase impregnated with Yb-diphthalocyanine was used.