Michael Bredol

Synthetic and natural carbons are widely used as carrier for electrodes in electrochemical applications. They need to have a controlled morphology in order to facilitate mass and charge transport, so the process of film formation is of uttermost importance. Here we show, how carbons (after proper preconditioning) can be codeposited with an ionomer by electrophoretic deposition, a method that does allow full control of deposition conditions during the process. In view of potential applications, we focus on the direct deposition on proton‐conducting membranes. Ionomers and membranes applied are based on established per‐fluorinated polyethylene with SO₃H‐terminated side chains (PFSA). Conditions for reproducible deposition are reported in terms of optimal charge on the carbon particles, field strength in the deposition cell and necessary deposition times for a given film thickness. Additionally, a horizontal cell arrangement is suggested to avoid gravitational effects.

This study investigated the ability of electrically conductive carbon rovings to detect cracks in textile-reinforced concrete (TRC) structures. The key innovation lies in the integration of carbon rovings into the reinforcing textile, which not only contributes to the mechanical properties of the concrete structure but also eliminates the need for an additional sensory system, such as strain gauges, to monitor the structural health. Carbon rovings are integrated into a grid-like textile reinforcement that differs in binding type and dispersion concentration of the styrene butadiene rubber (SBR) coating. Ninety final samples were subjected to a four-point bending test in which the electrical changes of the carbon rovings were measured simultaneously to capture the strain. The mechanical results show that the SBR50-coated TRC samples with circular and elliptical cross-sectional shape achieved, with 1.55 kN, the highest bending tensile strength, which is also captured with a value of 0.65 Ω by the electrical impedance monitoring. The elongation and fracture of the rovings have a significant effect on the impedance mainly due to electrical resistance change. A correlation was found between the impedance change, binding type and coating. This suggests that the elongation and fracture mechanisms are affected by the number of outer and inner filaments, as well as the coating.

The sensitive detection of singlet oxygen (¹O₂) is one key issue in various photochemical analyses, reactions, and processes; it is indispensable for designing catalysts for photodynamic therapies. Corresponding fluorescence-based organic ¹O₂ monitor luminophores may be equipped with rare-earth complexes with several intrinsic advantages. The design of the necessary ligands being a tedious, time-consuming effort, often involving empirical guesswork, we decided to support our experimental work with quantum chemical calculations. Hence, next to the experimental core, this paper suggests the additional use of time-dependent density functional theory (TDDFT) on suitable, free β-diketonate ligands to devise corresponding Eu³⁺ complexes as ¹O₂ probes eventually; the free ligand calculations obviously allow profoundly reduced computational efforts. Novel β-diketonate-substituted dimethyl anthracene complexes of Eu³⁺, Tb³⁺, and Gd³⁺ and their endoperoxidized descendants were thus synthesized, compared to known related complexes and analyzed with regard to their electronic characteristics; in addition, spectroscopy of a Eu³⁺ complex with ancillary epoxiphenanthroline for subsequent attachment to biological substrates featuring -NH₂ or -SH groups was included. The spectroscopic determination of the decisive lowest triplet (T₁) states of the Gd complexes could be matched by the Tamm-Dancoff approximation (TDA)/TDDFT calculations on the free ligands satisfactorily if suitable functionals were applied. Most significantly, the results suffice to describe the luminescence "switch-on" mechanism of this complex in the presence of ¹O₂.

A general procedure based on electrostatic self-assembly for preparing nanocomposites based on carbon nanotubes (CNTs) and ternary chalcogenide semiconductor nanoparticles is shown. This was achieved by surface functionalization of the single components through well-established protocols, for CNTs, and a transferable general strategy for the nanoparticles. Heterostructures were then synthesized through electrostatic interaction between oppositely charged components. Structural, colloidal, and optical properties were characterized by transmission electron microscopy, X-ray diffraction, infrared spectroscopy, dynamic light scattering, ζ-potential, and absorption- and (time-resolved) photoluminescence measurements. Interestingly, the nanocomposites showed a blue shift in their excitation and emission spectra when compared to the pure nanoparticles but only when analyzed in powder form. Further investigations in the form of density functional theory (DFT) calculations were performed to evaluate the origin of the change in the optical properties.

The linear photochemical response of materials depends on two critical parameters: the size of the optical band gap determines the onset of optical excitation, whereas the absolute energetic positions of the band edges define the reductive or oxidative character of photo-generated electrons and holes. Tuning these characteristics is necessary for many potential applications and can be achieved through changes in the bulk composition or particle size, adjustment of the surface chemistry or the application of electrostatic fields. In this contribution the influence of surface chemistry and fields is investigated systematically with the help of standard DFT calculations for a typical case, namely composites prepared from ZnS quantum dots and functionalized carbon nanotubes. After comparing results with existing qualitative and quantitative experimental data, it is shown conclusively, that the details of the surface chemistry (especially defects) in combination with electrostatic fields have the largest influence. In conclusion, the development of novel or improved photoresponsive materials therefore will have to integrate a careful analysis of the interplay between surface chemistry, surface charges and interaction with the material environment or substrate.