The importance of anchoring ligands of binuclear sensitizers on electron transfer processes and photovoltaic action in dye-sensitized solar cells.

The relatively low photon-to-current conversion efficiency of dye-sensitized solar cells is their major drawback limiting widespread application. Light harvesting, followed by a series of electron transfer processes, is the critical step in photocurrent generation. An in-depth understanding and fine optimization of those processes are crucial to enhance cell performance. In this work, we synthesize two new bi-ruthenium sensitizers with extended anchoring ligands to gain insight into underlying processes determining photovoltaic action mechanisms. The structure of the compounds has been confirmed, and their properties have been thoroughly examined by various techniques such as NMR, IR, elemental analysis UV-Vis, cyclic voltammetry, and electroabsorption. The experimental characterization has been supported and developed via extensive quantum-chemical calculations, giving a broad view of the presented molecules' properties. Finally, the DSSC devices have been assembled utilizing obtained dyes. The photovoltaic and EIS measurements, combined with performed calculations and fundamental dyes characterization, unraveled an intramolecular electron transfer as an initial step of the electron injection process at the dye/semiconductor interface. The overall photovoltaic action mechanism has been discussed. Our study demonstrates the significance of the anchoring group architecture in the molecular design of new sensitizers for DSSC applications.

Electronic States of Tris(bipyridine) Ruthenium(II) Complexes in Neat Solid Films Investigated by Electroabsorption Spectroscopy.

We present the electric field-induced absorption (electroabsorption, EA) spectra of the solid neat films of tris(bipyridine) Ru(II) complexes, which were recently functionalized in our group as photosensitizers in dye-sensitized solar cells, and we compare them with the results obtained for an archetypal [Ru(bpy)3]2+ ion (RBY). We argue that it is difficult to establish a unique set of molecular parameter values by discrete parametrization of the EA spectra under the Liptay formalism for non-degenerate excited states. Therefore, the experimental EA spectra are compared with the spectra computed by the TDDFT (time-dependent density-functional theory) method, which for the first time explains the mechanism of electroabsorption in tris(bipyridine) Ru complexes without any additional assumptions about the spectral lineshape of the EA signal. We have shown that the main EA feature, in a form close to the absorption second derivative observed in the spectral range of the first MLCT (metal-to-ligand charge transfer) absorption band in Ru(bpy)3(PF6)2, can be attributed to a delocalized and orbitally degenerate excited state. This result may have key implications for the EA mechanism in RBY-based systems that exhibit similar EA spectra due to the robust nature of MLCT electronic states in such systems.

Preparation and Characterization of Defective TiO2. The Effect of the Reaction Environment on Titanium Vacancies Formation.

Among various methods of improving visible light activity of titanium(IV) oxide, the formation of defects and vacancies (both oxygen and titanium) in the crystal structure of TiO2 is an easy and relatively cheap alternative to improve the photocatalytic activity. In the presented work, visible light active defective TiO2 was obtained by the hydrothermal reaction in the presence of three different oxidizing agents: HIO3, H2O2, and HNO3. Further study on the effect of used oxidant and calcination temperature on the physicochemical and photocatalytic properties of defective TiO2 was performed. Obtained nanostructures were characterized by X-ray diffractometry (XRD), specific surface area (BET) measurements, UV-Vis diffuse reflectance spectroscopy (DR-UV/Vis), photoluminescence spectroscopy (PL), X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) spectroscopy. Degradation of phenol as a model pollutant was measured in the range of UV-Vis and Vis irradiation, demonstrating a significant increase of photocatalytic activity of defective TiO2 samples above 420 nm, comparing to non-defected TiO2. Correlation of EPR, UV-Vis, PL, and photodegradation results revealed that the optimum concentration of HIO3 to achieve high photocatalytic activity was in the range of 20-50 mol%. Above that dosage, titanium vacancies amount is too high, and the obtained materials' photoactivity was significantly decreased. Studies on the photocatalytic mechanism using defective TiO2 have also shown that •O2- radical is mainly responsible for pollutant degradation.

The Quantum Efficiency Roll-Off Effect in Near-Infrared Organic Electroluminescent Devices with Iridium Complexes Emitters.

The electroluminescence quantum efficiency roll-off in iridium(III)-based complexes, namely Ir(iqbt)2(dpm) and Ir(iqbt)3 (iqbt = 1 (benzo[b]thiophen-2-yl)-isoquinolinate, dpm = 2,2,6,6-tetramethyl-3,5-heptanedionate) utilized as near-infrared emitters in organic light emitting diodes with remarkable external quantum efficiencies, up to circa 3%, 1.5% and 1%, are measured and analyzed. With a 5-6 weight% of emitters embedded in a host matrix, the double-layer solution-processed structure as well as analogous three-layer one extended by a hole-conducting film are investigated. The triplet-polaron, the Onsager electron-hole pair dissociation and the triplet-triplet annihilation approaches were used to reproduce the experimental data. The mutual annihilation of triplets in iridium emitters was identified as prevailingly controlling the moderate roll-off, with the interaction between those of iridium emitters and host matrixes found as being less probable. Following the fitting procedure, the relevant rate constant was estimated to be ( 0.5 - 12 ) × 10 - 12 cm3/s, values considered to be rather too high for disordered organic systems, which was assigned to the simplicity of the applied model. A coexistence of some other mechanisms is therefore inferred, ones, however, with a less significant contribution to the overall emission quenching.

Hybrid TiO2-Polyaniline Photocatalysts and their Application in Building Gypsum Plasters.

Hybrid materials of conjugated polymer and titanium(IV) oxide have attracted considerable attention concerning their potential benefits, including (i) efficient exploitation of visible light, (ii) a high adsorption capacity for organic contaminants, (iii) and effective charge carriers separation. The new class of the photocatalysts is promising for the removal of environmental pollutants in both aqueous and gaseous phases. For the first time, in this study, the polyaniline (PANI)-TiO2 hybrid composite was used for the degradation of phenol in water and toluene in the gas phase. Polyaniline-TiO2 was prepared by the in situ polymerization of aniline on the TiO2 surface. The obtained hybrid material was characterized by diffuse reflectance spectroscopy (DR/UV-Vis), X-ray diffraction (XRD), fast-Fourier transformation spectroscopy (FTIR), photoluminescence (PL) spectroscopy, microscopy analysis (SEM/TEM), and thermogravimetric analysis (TGA). An insight into the mechanism was shown based on the photodegradation analysis of charge carrier scavengers. Polyaniline is an efficient TiO2 photosensitizer for photodegradation in visible light (λ > 420 nm). The trapping experiments revealed that mainly h+ and ˙OH were the reactive oxygen species that were responsible for phenol degradation. Furthermore, the PANI-TiO2 hybrid nanocomposite was used in gypsum plaster to study the self-cleaning properties of the obtained building material. The effect of PANI-TiO2 content on the hydrophilic/hydrophobic properties and crystallographic structure of gypsum was studied. The obtained PANI-TiO2-modified gypsum plaster had improved photocatalytic activity in the reaction of toluene degradation under Vis light.

Improved degradation of etodolac in the presence of core-shell ZnFe2O4/SiO2/TiO2 magnetic photocatalyst.

In the present study, susceptibility to photocatalytic degradation of etodolac, 1,8-diethyl-1,3,4,9 - tetrahydro pyran - [3,4-b] indole-1-acetic acid, which is a non-steroidal anti-inflammatory drug frequently detected in an aqueous environment, was for the first time investigated. The obtained p-type TiO2-based photocatalyst coupled with zinc ferrite nanoparticles in a core-shell structure improves the separation and recovery of nanosized TiO2 photocatalyst. The characterization of ZnFe2O4/SiO2/TiO2, including XRD, XPS, TEM, BET, DR/UV-Vis, impedance spectroscopy and photocatalytic analysis, showed that magnetic photocatalyst containing anatase phase revealed markedly improved etodolac decomposition and mineralization measured as TOC removal compared to photolysis reaction. The effect of irradiation and pH range on photocatalytic decomposition of etodolac was studied. The most efficient degradation of etodolac was observed under simulated solar light for a core-shell ZnFe2O4/SiO2/TiO2 magnetic photocatalyst at pH above 4 (pKa = 4.7) and below 7. The irradiation of etodolac solution in a broader light range revealed a synergetic effect on its photodegradation performance. After only 20 min of degradation, about 100% of etodolac was degraded. Based on the photocatalytic analysis in the presence of scavengers and HPLC analysis, the transformation intermediates and possible photodegradation pathways of etodolac were studied. It was found that ∙O2- attack on C2-C3 bond inside pyrrole ring results mostly in the hydroxylation of the molecule, which next undergoes -CH2COOH detachment to give 1,9-diethyl-3,4-dihydro-pyrano[3,4-b]indol-4a-ol. The obtained compound should further undergo subsequent hydropyran and pyrrole ring breaking to give a family of benzene derivatives.