Publikationen

Multi-walled carbon nanotubes doped with sulfur and nitrogen (S-N-MWCNTs) were grown onto silicon/silicon oxide wafer by means of chemical vapor deposition upon decomposition of dimethyl sulfoxide (DMSO) and acetonitrile (ACN) in presence of catalyst. The S-N-MWCNTs were characterized by scanning electron microscopy combined with energy dispersive X-ray spectroscopy. The findings demonstrate that S-N-MWCNTs exhibit bamboo-shaped nanostructure, quite similar to pure nitrogen-doped carbon nanotubes. The S-N-MWCNTs were investigated with respect to their electrochemical response to ferrocyanide/ferricyanide, [Fe(CN)6]4-/3- in potassium chloride aqueous solutions by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. The recorded CVs demonstrate strong dependence of electrochemical response, electron transfer kinetics, and sensitivity of S-N-MWCNTs on concentration of decomposed DMSO precursor. Namely, upon increasing concentration of decayed DMSO up to 2% wt. the current density, the electron transfer kinetics, and the sensitivity of S-N-MWCNTs toward [Fe(CN)6]4-/3- tend to enhance. The extracted EIS results approve that when DMSO reaches the optimum concentration of 2% wt. the barrier for electron transfer decreases significantly leading, consequently, to faster electron transfer kinetics. The S-N-MWCNTs exhibit considerable stability and excellent reproducibility, and thus it can be considered suitable analytical tool for detection of redox systems at micromolar level.

Phosphoric acid is commonly known either as a neutral molecule or as an anion (phosphate). We theoretically confirm by ab initio molecular dynamics simulations (AIMD) that a cationic form H4PO4+ coexists with the anionic form H2PO4- in the same salt. This paradoxical situation is achieved by partial substitution of Cs+ by H4PO4+ in CsH2PO4. Thus, HnPO4 acts simultaneously as both the positive and the negative ion of the salt. We analyze the dynamical protonation pattern within the unusual hydrogen bond network that is established between the ions. Our AIMD simulations show that a conventional assignment of protonation states of the phosphate groups is not meaningful. Instead, a better description of the protonation situation is achieved by an efficiently fractional assignment of the strongly hydrogen-bonded protons to both its nearest and next-nearest oxygen neighbors.

By a well known theorem of Robbins, a graph G has a strongly connected orientation if and only if G is 2-edge-connected and it is easy to find, in linear time, either a cut edge of G or a strong orientation of G. A result of Durand de Gevigney shows that for every it is NP-hard to decide if a given graph G has a k-strong orientation. Thomassen showed that one can check in polynomial time whether a given graph has a 2-strong orientation. This implies that for a given digraph D we can determine in polynomial time whether we can reorient (=reverse) some arcs of to obtain a 2-strong digraph. This naturally leads to the question of determining the minimum number of such arcs to reverse before the resulting graph is 2-strong. In this paper we show that finding this number is NP-hard. If a 2-connected graph G has no 2-strong orientation, we may ask how many of its edges we may orient so that the resulting mixed graph is still 2-strong. Similarly, we may ask for a 2-edge-connected graph G how many of its edges we can orient such that the resulting mixed graph remains 2-arc-strong. We prove that when restricted to graphs satisfying suitable connectivity conditions, both of these problems are equivalent to finding the minimum number of edges we must double in a 2-edge-connected graph in order to obtain a 4-edge-connected graph. Using this, we show that all these three problems are NP-hard. Finally, we consider the operation of deorienting an arc uv of a digraph D meaning replacing it by an undirected edge between the same vertices. In terms of connectivity properties, this is equivalent to adding the opposite arc vu to D. We prove that for every it is NP-hard to find the minimum number of arcs to deorient in a digraph D in order to obtain an ℓ-strong digraph.

Selecting the right cathode material is a key component to achieving high-energy and long-lifespan aqueous zinc-ion batteries (AZIBs); however, the development of cathode materials still faces serious challenges due to the high polarization of Zn2+. In this work, MnV12O31&hahog;10H2O (MnVO) synthesized via a one-step hydrothermal method is proposed as a promising cathode material for AZIBs. Because the stable layered structure and hieratical morphology of MnVO provide a large layer space for rapid ion transports, this material exhibits high specific capacity (433 mAh g−1 at 0.1 A g−1), an outstanding long-term cyclability (5000 cycles at a current density of 3 A g−1), and an excellent energy density (454.65 Wh kg−1). To illustrate the intercalation mechanism, ex situ X-Ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy are adopted, uncovering an H+/Zn2+ dual-cation co-intercalation processes. In addition, density-functional theory calculation analysis shows that MnVO has a delocalized electron cloud and the diffusion energy barrier of Zn2+ in MnVO is low, which promotes the Zn2+ transport and consequently improves the reversibility of the battery upon deep cycling. The key and enlightening insights are provided in the results for designing high-performance vanadium-oxide-based cathode materials for AZIBs.

Relaxation and diffusion measurements were carried out on single and binary liquids filling the pore space of controlled porous glass Vycor with an average pore size of about 4 nm. The dispersion of the longitudinal relaxation time T1 is discussed as a means to identify liquid-surface interaction based on existing models developed for metal-free glass surfaces. In addition, the change of T1 and T2 with respect to their bulk values is discussed, in particular T2 serves as a probe for the strength of molecular interactions. As the native glass surface is polar and contains a large amount of hydroxyl groups, a pronounced interaction of polar and protic adsorbate liquids is expected; however, the T1 dispersion, and the corresponding reduction of T2, are also observed for non-polar liquids such as alkanes and cyclohexane. Deuterated liquids are employed for simplifying data analysis in binary systems, but also for separating the respective contributions of intra- and intermolecular interactions to the overall relaxation rate. Despite the lack of paramagnetic impurities in the glass material, 1H and 2H relaxation dispersions of equivalent molecules are frequently found to differ from each other, suggesting intermolecular relaxation mechanisms for the 1H nuclei. The variation of the T1 dispersion when comparing single and binary systems gives clear evidence for the preferential adsorption of one of the two liquids, suggesting complete phase separation in several cases. Measurement of the apparent tortuosity by self-diffusion experiments supports the concept of a local variation of sample composition within the porespace.