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- ItemSynthesis and characterization of new photoswitchable azobenzene-containing poly(ε-caprolactones)(London : RSC Publishing, 2016) Appiah, Clement; Siefermann, Katrin R.; Jorewitz, Marcel; Barqawi, Haitham; Binder, Wolfgang H.A novel and efficient strategy in obtaining series of mono- and bi-armed azobenzene-containing poly(ε-caprolactone)s is described, starting from a commercially available azobenzene dye via azide/alkyne-“click”-reactions. The attachment of alkyne-telechelic poly(ε-caprolactone)s (1 kDa and 3 kDa), followed by chromatographic separation, allowed the attachment of either one or two PCl-chains to either side of the azobenzene-dye. The resulting mono- and bi-armed photo-switchable polymers are fully characterized by 2D-NMR techniques and show a high thermal stability. Additionally liquid chromatography at critical conditions (LCCC) coupled to ESI-TOF allowed us to prove the presence of either one or two polymer chains affixed onto the central azobenzene dye.
- ItemInterconnected electrocatalytic Pt-metal networks by plasma treatment of nanoparticle-peptide fibril assemblies(London : RSC Publishing, 2019) Bandak, J.; Petzold, J.; Hatahet, H.; Prager, A.; Kersting, B.; Elsner, Ch.; Abel, B.Noble metal catalysts possess outstanding catalytic behaviors in organic reactions, photocatalysis, electrocatalysis and many other applications. Peptide fibrils are used for the controllable nanostructuring of metal nanoparticles with specific sizes, shapes and high-surface area structures. The degradation of these fibrils with O2-plasma yields interconnected networks of nanoparticles, similar to metallic nanowires. Herein, platinum nanoparticles (Pt-NPs) were synthesized by reduction using VUV excimer radiation. The particle size was characterized by dynamic light scattering (DLS). Due to agglomeration, the metal nanoparticles were stabilized using poly(vinyl pyrrolidone) (PVP) and the same synthesis procedure. The influence of the polymer PVP molecular weight (Mwt), PVP concentration (Cp) and VUV irradiation time on platinum nanoparticle size was investigated. Small (2–3 nm) Pt-NPs are formed in the case of PVP with Mwt = 10 000 g mol−1. With increasing PVP Mwt, decreasing PVP concentration and shorter irradiation times, larger sized nanoparticles appear. The applicability of templated platinum nanoparticles, both the PVP-stabilized and non-stabilized Pt-NPs, immobilized via electrostatic interactions on the solid phase-synthesized aniline-GGAAKLVFF (AFP) peptide fibrils was investigated to serve as possible electrode material. The plasma treatment of the nanoparticle-fibril-assemblies was also studied as a novel technique. The Pt-NPs-AFP fibrils and the PVP-stabilized-Pt-NPs-AFP fibrils nanohybrids were employed to modify electrodes and then subjected to O2-plasma treatment. These O2-plasma treated/modified electrodes exhibited high electrocatalytic activities towards oxygen reduction in cyclic voltammetry measurements. Thus, the aforementioned nanocomposites hold great potential for polymer electrolyte fuel cells and other electrochemical applications in miniature devices and microfluidic chips.
- ItemPhotocatalytic degradation and toxicity evaluation of diclofenac by nanotubular titanium dioxide–PES membrane in a static and continuous setup(London : RSC Publishing, 2015) Fischer, K.; Kühnert, M.; Gläser, R.; Schulze, A.Diclofenac is a commonly used anti-inflammatory drug, which has been found in surface waters. Advanced oxidation processes (AOPs) seem to be the most suitable technique to prevent the entry of diclofenac and other pollutants into surface waters. TiO2 is especially reliable in mineralizing many organic molecules. The combination of TiO2 nanotubes with a polymer microfiltration membrane (polyethersulfone, PES) showed high photocatalytic activity by degrading diclofenac combined with an excellent membrane performance and long-term stability. By continuously degrading pollutants from water via a cross-flow setup, the molecules to be degraded are transported right to the membrane surface so that the overall reaction rate is increased. The toxicity of diclofenac was reduced by photocatalysis and photolysis; however, photocatalysis had greater impact. Moreover, the complete degradation of pollutants is very important to avoid highly toxic intermediate products.
- ItemDimethyl carbonate synthesis from carbon dioxide using ceria–zirconia catalysts prepared using a templating method: characterization, parametric optimization and chemical equilibrium modeling(London : RSC Publishing, 2016) Kumar, Praveen; With, Patrick; Srivastava, Vimal Chandra; Shukla, Kartikeya; Gläser, Roger; Mishra, Indra ManiIn this paper, a series of CexZr1−xO2 solid solution spheres were synthesized by exo- and endo-templating methods and tested for dimethyl carbonate (DMC) synthesis using direct conversion of CO2. The synthesized catalysts were characterized by X-ray diffraction (XRD), N2-physisorption, scanning electron microscopy (SEM), and CO2/NH3-temperature-programmed desorption (TPD). Formation of CexZr1−xO2 solid solutions with tetragonal and cubic crystal structures depending on cerium/zirconium compositions was confirmed by XRD analysis. The specific surface area of the mixed oxide decreased and the average pore diameter increased with an increase in the ceria content, with the exception of the mixed oxides with x = 0.4–0.5 i.e. Ce0.4Zr0.6O2 and Ce0.5Zr0.5O2. The basic and acidic site density of the synthesized catalysts was in the order: ZrO2 < CeO2 < Ce0.5Zr0.5O2, and the basic and acidic site density per unit area followed the same order. The best Ce0.5Zr0.5O2 catalyst was further used for the optimization of reaction conditions such as reaction time, reaction temperature, catalyst dose and reusability for DMC synthesis. Furthermore, study of chemical equilibrium modeling was done using the Peng–Robinson–Stryjek–Vera equation of state (PRSV-EoS) along with the van der Waals one-fluid reaction condition so as to calculate change of Gibbs free energy (ΔG°) and heat of reaction (ΔH°).
- ItemFacile and scalable synthesis of sub-micrometer electrolyte particles for solid acid fuel cells(London : RSC Publishing, 2018) Lohmann-Richters, F.P.; Odenwald, C.; Kickelbick, G.; Abel, B.; Varga, Á.Nanostructuring fuel cell electrodes is a viable pathway to reach high performance with low catalyst loadings. Thus, in solid acid fuel cells, small CsH2PO4 electrolyte particles are needed for the composite powder electrodes as well as for thin electrolyte membranes. Previous efforts have resulted in significant improvements in performance when using sub-micrometer CsH2PO4 particles, but laborious methods with low throughput were employed for their synthesis. In this work, we present a simple, robust, and scalable method to synthesize CsH2PO4 particles with diameters down to below 200 nm. The method involves precipitating CsH2PO4 by mixing precursor solutions in alcohol in the presence of a dispersing additive. The influence of the concentrations, the batch size, the solvent, and the mixing process is investigated. The particle size decreases down to 119 nm with increasing amount of dispersing additive. Mixing in a microreactor leads to a narrower particle size distribution. The particle shape can be tuned by varying the solvent. The ionic conductivity under solid acid fuel cell conditions is 2.0 × 10-2 S cm-1 and thus close to that of CsH2PO4 without dispersing additive.
- ItemB12X11(H2)−: exploring the limits of isotopologue selectivity of hydrogen adsorption(London : RSC Publishing, 2021) Wulf, Toshiki; Warneke, Jonas; Heine, ThomasWe study the isotopologue-selective binding of dihydrogen at the undercoordinated boron site of B12X11− (X = H, F, Cl, Br, I, CN) using ab initio quantum chemistry. With a Gibbs free energy of H2 attachment reaching up to 80 kJ mol−1 (ΔG at 300 K for X = CN), these sites are even more attractive than most undercoordinated metal centers studied so far. We thus believe that they can serve as an edge case close to the upper limit of isotopologue-selective H2 adsorption sites. Differences of the zero-point energy of attachment average 5.0 kJ mol−1 between D2 and H2 and 2.7 kJ mol−1 between HD and H2, resulting in hypothetical isotopologue selectivities as high as 2.0 and 1.5, respectively, even at 300 K. Interestingly, even though attachment energies vary substantially according to the chemical nature of X, isotopologue selectivities remain very similar. We find that the H–H activation is so strong that it likely results in the instantaneous heterolytic dissociation of H2 in all cases (except, possibly, for X = H), highlighting the extremely electrophilic nature of B12X11− despite its negative charge. Unfortunately, this high reactivity also makes B12X11− unsuitable for practical application in the field of dihydrogen isotopologue separation. Thus, this example stresses the two-edged nature of strong H2 affinity, yielding a higher isotopologue selectivity on the one hand but risking dissociation on the other, and helps define a window of adsorption energies into which a material for selective adsorption near room temperature should ideally fall.
- ItemSystematic tuning of segmented magnetic nanowires into three-dimensional arrays of 'bits'(London : RSC Publishing, 2017) Bochmann, S.; Fernandez-Pacheco, A.; Mačković, M.; Neff, A.; Siefermann, K.R.; Spiecker, E.; Cowburn, R.P.; Bachmann, J.A method is presented for the preparation of a three-dimensional magnetic data storage material system. The major ingredients are an inert nanoporous matrix prepared by anodization and galvanic plating of magnetic and non-magnetic metals in wire shape inside the cylindrical pores. The individual nanomagnets consist of a nickel-cobalt alloy, the composition of which is tuned systematically by adjusting the electrolytic bath composition at one optimal applied potential. The lowest magnetocrystalline anisotropy is obtained at the composition Ni60Co40, as quantified by superconducting quantum interference device magnetometry. Wires of this composition experience a pinning-free propagation of magnetic domain walls, as determined by single-wire magneto-optical Kerr effect magnetometry. Adding copper into the electrolyte allows one to generate segments of Ni60Co40 separated by non-magnetic copper. The segment structure is apparent in individual nanowires imaged by scanning electron microscopy, UV-photoelectron emission microscopy, and transmission electron microscopy. The single-domain structure of the wire segments is evidenced by magnetic force microscopy.