Cellulose-based materials in tailoring a novel defective titanium­carbon­phosphorus hybrid composites for highly efficient photocatalytic activity.

Until now, black titania has attracted much interest as a potential photocatalyst. In this contribution, we report the first demonstration of the effective strategy to fundamentally improve the photocatalytic performance using a novel sustainable defective titanium­carbon-phosphorous (TCPH) hybrid nanocomposite. The prepared TCPH was used for photocatalytic degradation of the main organic pollutants, which is methyl orange (MO) dye. The physico-chemical properties of as-prepared samples were characterized by various techniques to observe the transformations after carbonization and the interaction between different composite phases. The existence of Ti+3 and oxygen vacancies at the surface, and a notable increase in surface area, are all demonstrated by TCPH, together with the distinct core-shell structure. These unique properties exhibit excellent photocatalytic performance due to the boosted charge transport and separation. The highest degradation efficiency of methyl orange (MO) was attained in the case of TCPH when compared with titanium-cellulose-phosphorous (TCeP) and titanium­carbon-phosphorous (TCPN). Accordingly, the highest degradation efficiency was achieved by applying the optimal operational conditions of 1 g/L of TCPH catalyst, 10 mg/L of MO, pH of 7 and the temperature at 25 ± 3 °C after 3 min under LED lamp (365 nm) with light intensity 100 mW/cm2. The degradation mechanism was investigated, and the trapping tests showed the dominance of hydroxyl radicals in the degradation of MO. TCPH showed high stability under a long period of operation in five consecutive cycles, which renders the highly promising on an industrial scale. The fabrication of highly active defective titanium­carbon-phosphorous opens new opportunities in various areas, including water splitting, and CO2 reduction.

Comparative Studies of g-C3N4 and C3N3S3 Organic Semiconductors-Synthesis, Properties, and Application in the Catalytic Oxygen Reduction.

Exfoliated g-C3N4 is a well-known semiconductor utilized in heterogenous photocatalysis and water splitting. An improvement in light harvesting and separation of photogenerated charge carriers may be obtained by polymer doping with sulfur. In this work, we incorporate sulfur into the polymer chain by chemical polymerization of trithiocyanuric acid (C3N3S3H3) to obtain C3N3S3. The XRD measurements and TEM images indicated that C3N3S3, in contrast to g-C3N4, does not exist in the form of a graphitic structure and is not exfoliated into thin lamellas. However, both polymers have similar optical properties and positions of the conduction and valence bands. The comparative studies of electrochemical oxygen reduction and hydrogen evolution indicated that the overpotentials for the two processes were smaller for C3N3S3 than for g-C3N4. The RDE experiments in the oxygen-saturated solutions of 0.1 M NaOH have shown that O2 is electrochemically reduced via the serial pathway with two electrons involved in the first step. The spectroscopic experiments using NBT demonstrated that both polymers reveal high activity in the photocatalytic reduction of oxygen to superoxide anion radical by the photogenerated electrons.

Enhanced Performance of Camphorsulfonic Acid-Doped Perovskite Solar Cells.

High-quality perovskite film with large grains and therefore reduced grain boundaries plays a significant role in improving the power conversion efficiency (PCE) and ensuring good long-term stability of the perovskite solar cells. In this work, we found that adding camphorsulfonic acid (CSA), a Lewis base, to the perovskite solution results in the crystallization of larger perovskite grains. By varying the concentration of CSA, we found that the optimal concentration of the additive is 1 mg/mL, which leads to an 20% increase in PCE of the cells compared to the reference CSA-free cell. Interestingly, we observed that the PCE of cells with an excess of CSA was initially poor, but may increase significantly over time, possibly due to CSA migration to the hole-transporting layer, leading to an improvement in its conductivity.

Mono- and Di-Pyrene [60]Fullerene and [70]Fullerene Derivatives as Potential Components for Photovoltaic Devices.

In the present work, we report the successful synthesis and characterization of six (two new) fullerene mono- and di-pyrene derivatives based on C60 and C70 fullerenes. The synthesized compounds were characterized by spectral methods (ESI-MS, 1H-NMR, 13C-NMR, UV-Vis, FT-IR, photoluminescence and photocurrent spectroscopy). The energy of HOMO and LUMO levels and the band gaps were determined from cyclic voltammetry and compared with the theoretical values calculated according to the DFT/B3LYP/6-31G(d) and DFT/PBE/6-311G(d,p) approach for fully optimized molecular structures at the DFT/B3LYP/6-31G(d) level. Efficiency of solar cells made of PTB7: C60 and C70 fullerene pyrene derivatives were analyzed based on the determined energy levels of the HOMO and LUMO orbitals of the derivatives as well as the extensive spectral results of fullerene derivatives and their mixtures with PTB7. As a result, we found that the electronic and spectral properties, on which the efficiency of a photovoltaic cell is believed to depend, slightly changes with the number and type of pyrene substituents on the fullerene core. The efficiency of constructed solar cells largely depends on the homogeneity of the photovoltaic layer, which, in turn, is a derivative of the solubility of fullerene derivatives in the solvent used to apply these layers by spincoating.

A comprehensive optical and electrical study of unsymmetrical imine with four thiophene rings and their binary and ternary compositions with PTB7 and PC70BM towards organic photovoltaics.

A new unsymmetrical imine with four thiophene rings was synthesized in a one-step reaction, starting from the commercially available and relatively inexpensive reagents. The obtained imine in the form of thin films exhibited photoluminescence properties in the 1.8-2.4 eV energy range and a photoluminescence lifetime of about 0.3 ns. The HOMO and LUMO levels of the imine determined by cyclic voltammetry were at about -5.19 eV and -3.05 eV, respectively. The density functional theory was applied to calculate the geometric and electronic structure of the imine. The UV-Vis spectra showed that the absorption range of the imine overlaps with that of PC70BM, and the absorption peak at the maximum of the imine at 424 nm is located between the two maxima at 404 nm and 461 nm of the fullerene derivative. The electron acceptor and donor activity of the imine was tested in the solar cell architecture: glass/ITO/PEDOT:PSS/active layer/In/Al. The best photovoltaic parameters, with very good reproducibility for each 8 pixels in the cell, were found for the active layer based on ternary mixture PTB7:PC70BM:imine at a weight ratio 8 : 13 : 1, with the power conversion efficiency of about 4%. The external quantum efficiency of devices with the imine was found to be about 40% at 3.3 eV. The thermal imaging together with the recorded current response at increasing potential showed that the presence of imine in the composition has a beneficial impact in terms of current flow stability at temperatures above 200 °C, compared to two component layers with the same imine as an additive.

Mixed solutions of silver cation and chloride anion in acetonitrile: voltammetric and EQCM study.

Electrochemical behavior of Pt and Au electrodes in acetonitrile solutions at different concentration ratios of Cl(-) and Ag(+) ions was studied by cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM). The composition of the mixed silver chloride solutions, i.e. the amount of each component of the system (solid AgCl and solute species: Ag(+), Cl(-), AgCl(2)(-)), is governed by the solubility product of AgCl and the stability constant of AgCl(2)(-)complex and depends strongly on the ratio of the total concentrations of chloride and silver ions. In this work we analyze in detail the influence of the Cl(-)/Ag(+) concentration ratio on the value of equilibrium electrode potential and the shape of cyclic voltammograms. We explain the complicated shapes of the experimental curves observed at different concentration ranges, propose the mechanisms of the processes occurring at the electrode and substantiate them by EQCM data.

Electrodeposition of poly(N-vinylcarbazole) at the three-phase junction. Formation of very different polymer structures.

Poly(N-vinylcarbazole) films can be deposited at the three-phase boundary when the organic phase contains only monomer, N-vinylcarbazole, while the aqueous phase contains supporting electrolyte. A cylindrical platinum microelectrode is immersed into the two-liquid system in such a way that a part of it is located in one liquid and the other part resides in the second liquid. The thickness of the reaction layer, or the width of the microelectrode zone where the polymer grows, depends on the kind of ions present in the aqueous phase and the time of the experiment. The structure of the deposited polymer may be very different and depends on the distance from the three-phase boundary and the type of the anion present in the aqueous phase. The key parameters here are the local electrode potential and the local concentration of the anions. The list of obtained polymer structures includes, among others, arrays of perfectly arranged deep oval channels and groups of microcrystals. The porosity of the polymer deposits increases with the distance from the aqueous phase.

Time-temperature superposition for viscoelastic properties of regioregular poly(3-hexylthiophene) films.

Shear moduli were determined for chemically polymerized and solvent cast regioregular poly(3-hexylthiophene) films, using thickness shear mode acoustic wave resonators. The results are strikingly different to those for electropolymerized regiorandom poly(3-hexylthiophene) films. The time scale of the measurement was varied directly by use of higher harmonics of the acoustic wave resonator and indirectly via temperature. The significant variations in shear modulus with effective time scale can be "normalized"onto a stress master relaxation curve by using the concept of time-temperature superposition; this is the first time this has been demonstrated for electroactive films. The shift factors required to effect this normalization do not follow the classical Williams-Landel-Ferry (WLF) equation developed for long-range backbone motions of bulk polymers. Instead, they follow an Arrhenius-like behavior, commonly used to describe secondary motions of polymer side-chains. The activation enthalpy associated with this is independent of applied potential, is the same as for as cast (undoped) films, and is similar to that for rotation about a carbon-carbon single bond. These all point to the hexyl side-chains as the origins of the observed phenomena, consistent with the "melting point" separating two temperature-dependent phases and with the different molecular packing arrangements that would necessarily apply to regioregular and regiorandom materials.

Dynamics of regioregular conducting polymer electrodes in response to electrochemical stimuli.

We report thickness shear mode resonator acoustic wave data for films of regioregular poly(3-hexylthiophene) films exposed to acetonitrile solutions of LiClO4. Both the current- and acoustic wave-responses to constant (or slowly swept) potential show different regimes, whose characteristics, which are quite different to those of regiorandom electropolymerized films, can be interpreted in terms of crystalline and non-crystalline material. Oxidation of crystalline material, which occurs at low potentials, is dominated by anion transfer; as a result of the associated electrostatic effects, the film stiffens. Oxidation of non-crystalline material, which occurs at more positive potentials, involves significant solvent transfer; the solvent softens the film. We have been able to determine film thickness changes and shear modulus components (based on a homogeneous film model) (i) as functions of potential (ie. charge state) and of temperature at fixed potential, and (ii) as a function of time following a potential step. In each case, we have been able to rationalise the electrochemical and viscoelastic phenomena in terms of electrochemically controlled film composition, of which the most significant component is solvation state.