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Tsierkezos, Nikos; Freiberger, Emma; Ritter, Uwe; Krischok, Stefan; Ullmann, Fabian; Köhler, Michael
Application of nitrogen-doped multi-walled carbon nanotubes decorated with gold nanoparticles in biosensing. - In: Journal of solid state electrochemistry, ISSN 1433-0768, Bd. 27 (2023), 10, S. 2645-2658

Novel films consisting of nitrogen-doped multi-walled carbon nanotubes (N-MWCNTs) were fabricated by means of chemical vapor deposition technique and decorated with gold nanoparticles (AuNPs) possessing diameter of 14.0 nm. Electron optical microscopy analysis reveals that decoration of N-MWCNTs with AuNPs does not have any influence on their bamboo-shaped configuration. The electrochemical response of fabricated composite films, further denoted as N-MWCNTs/AuNPs, towards oxidation of dopamine (DA) to dopamine-o-quinone (DAQ) in the presence of ascorbic acid (AA) and uric acid (UA) was probed in real pig serum by means of cyclic voltammetry (CV) and square wave voltammetry (SWV). The findings demonstrate that N-MWCNTs/AuNPs exhibit slightly greater electrochemical response and sensitivity towards DA/DAQ compared to unmodified N-MWCNTs. It is, consequently, obvious that AuNPs improve significantly the electrochemical response and detection ability of N-MWCNTs. The electrochemical response of N-MWCNTs/AuNPs towards DA/DAQ seems to be significantly greater compared to that of conventional electrodes, such as platinum and glassy carbon. The findings reveal that N-MWCNTs/AuNPs could serve as powerful analytical sensor enabling analysis of DA in real serum samples.



https://doi.org/10.1007/s10008-023-05562-2
Schricker, Klaus; Diegel, Christian; Schmidt, Leander; Seibold, Marc; Friedmann, Hannes; Fröhlich, Fabian; Eichler, Stefan; Chen, Yunhui; Requardt, Herwig; Rack, Alexander; Bergmann, Jean Pierre
Understanding the formation of “false friends” (hidden lack of fusion defects) in laser beam welding by means of high-speed synchrotron X-ray imaging. - In: Welding in the world, ISSN 1878-6669, Bd. 67 (2023), 11, S. 2557-2570

This paper provides a fundamental understanding of “false friend” formation, i.e., hidden defects associated with lack of fusion, using an experimental setup that allowed an insight into the processing zone based on high-speed synchrotron X-ray imaging. The setup enabled the welding of a lap joint of AISI 304 high-alloy steel sheets (X5CrNi18-10/1.4301), with the ability to adjust different gap heights between top and bottom sheet (up to 0.20 mm) and to acquire high-speed X-ray images at 100 kHz simultaneously with the welding process. On this basis, a time-resolved description of the “false friend” formation can be provided by visualizing the interaction between keyhole and melt pool during laser welding and solidification processes within the gap area. The bridgeability of the gap was limited due to the gap height and insufficient melt supply leading to the solidification of the bridge. The distance between the solidified bridge and the keyhole increased with time, while the keyhole and melt pool dynamics initiated the formation of new melt bridges whose stability was defined by melt flow conditions, surface tension, and gap heights. The alternating formation and solidification of melt bridges resulted in entrapped areas of lacking fusion within the weld, i.e., “false friends.” Finally, based on the results of this study, a model concept is presented that concludes the main mechanisms of “false friend” formation.



https://doi.org/10.1007/s40194-023-01581-9
Stapf, Siegfried; Shikhov, Igor; Arns, Christoph; Gizatullin, Bulat; Mattea, Carlos
Dipolar NMR relaxation of adsorbates on surfaces of controlled wettability. - In: Magnetic resonance letters, ISSN 2772-5162, Bd. 3 (2023), 3, S. 220-231

In reservoir rocks, the term “ageing” refers to extended exposition to crude oil; a typically water-wet sandstone will then gradually become oil-wet as a consequence of the deposition of insoluble fractions of oil onto the surface grains. Rocks have been aged artificially by subjecting them to a bitumen solution at elevated temperature in order to achieve comparable surface properties for three different types of rock: Bentheimer, Berea Buff and Liège Chalk. Using saturated and aromatic model compounds as proxies for crude oil, the nuclear magnetic resonance (NMR) relaxation dispersion in native and aged rocks was compared and correlated to the properties of paramagnetic impurities in these rock types. Perfluorated liquids were found to follow the same trend as deuterated and naturally occurring oil components, suggesting they can be used as suitable tracers for wettability studies since the 19F nucleus is absent in natural sources. By combining electron paramagnetic resonance (EPR) and dynamic nuclear polarization (DNP) it becomes possible to identify and quantify the origin of the dominating relaxation processes between native and aged rocks, providing an alternative approach to assess wettability in natural rocks.



https://doi.org/10.1016/j.mrl.2023.02.001
Gizatullin, Bulat; Mattea, Carlos; Stapf, Siegfried
Radicals on the silica surface: probes for studying dynamics by means of fast field cycling relaxometry and dynamic nuclear polarization. - In: Magnetic resonance letters, ISSN 2772-5162, Bd. 3 (2023), 3, S. 256-265

Determining the dynamics of adsorbed liquids on nanoporous materials is crucial for a detailed understanding of interactions and processes on the solid-liquid interface in many materials and porous systems. Knowledge of the influence of the presence of paramagnetic species on the surface or within the porous matrices is essential for fundamental studies and industrial processes such as catalysts. Magnetic resonance methods, such as electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR) and dynamic nuclear polarization (DNP), are powerful tools to address these questions and to quantify dynamics, electron-nuclear interaction features and their relation to the physical-chemical parameters of the system. This paper presents an NMR study of the dynamics of polar and nonpolar adsorbed liquids, represented by water, n-decane, deuterated water and nonane-d20, on the native silica surface as well as silica modified with vanadyl porphyrins. The analysis of the frequency dependence of the nuclear spin-lattice relaxation time is carried out by separating the intra- and intermolecular contributions, which were analyzed using reorientations mediated by translational displacements (RMTD) and force-free-hard-sphere (FFHS) models, respectively.



https://doi.org/10.1016/j.mrl.2023.03.006
Zhang, Chenglin; Yan, Chengzhan; Jin, Rui; Hao, Jinhui; Xing, Zihao; Zhang, Peng; Wu, Yuhan; Li, Longhua; Zhao, Huaping; Wang, Shun; Shi, Weidong; Lei, Yong
Weak interaction between cations and anions in electrolyte enabling fast dual-ion storage for potassium-ion hybrid capacitors. - In: Advanced functional materials, ISSN 1616-3028, Bd. 33 (2023), 52, 2304086, S. 1-10

Identifying an effective electrolyte is a primary challenge for hybrid ion capacitors, due to the intricacy of dual-ion storage. Here, this study demonstrates that the electrochemical behavior of graphite oxide in ether-solvent electrolyte outperforms those in ester-solvent electrolytes for the cathode of potassium-ion hybrid capacitor. The experimental and theoretical assessments verify that the anion and cation are isolated effectively in dimethyl ether, endowing a weaker interaction between cations and anions compared to that of ester-solvent electrolytes, which facilitates the dual-ion diffusion and thus enhances the electrochemical performance. This result provides a rational strategy to realize high-rate cations and anions storage on the carbon cathode. Furthermore, a new low-cost and high-performance capacitor prototype, modified graphite oxide (MGO) cathode versus pristine graphite (PG) in ether-solvent electrolyte (MGOǁDMEǁPG), is proposed. It exhibits a high energy density of 150 Wh kg^−1cathode at a high power density of 21443 W kg^−1cathode (calculation based on total mass: 60 Wh kg^−1 at 8577 W kg^−1).



https://doi.org/10.1002/adfm.202304086
Tsierkezos, Nikos; Reddmann, Eike Felix; Ritter, Uwe
Synthesis and electrochemical properties of sulfur-nitrogen-doped multi-walled carbon nanotubes. - In: Fullerenes, nanotubes & carbon nanostructures, ISSN 1536-4046, Bd. 31 (2023), 11, S. 1082-1095

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.



https://doi.org/10.1080/1536383X.2023.2240916
Ritter, Uwe; Nikolenko, Andrii; Alieksandrov, Maksim; Strelchuk, Viktor; Chumachenko, Vasyl; Kutsevol, Nataliya; Scharff, Peter; Prylutskyy, Yu I.
Structural and optical properties of C70 fullerenes in aqueous solution. - In: Fullerenes, nanotubes & carbon nanostructures, ISSN 1536-4046, Bd. 31 (2023), 10, S. 983-988

The simple method of preparation of highly stable and purified C70 fullerene aqueous solution (C70FAS) is proposed. The features of structural stabilization of C70 fullerenes in an aqueous solution by studying their structural and optical properties using Raman, photoluminescence, infrared reflection-absorption, UV-VIS absorption, and dynamic light scattering spectroscopy methods were analyzed. The experimental results showed that the most likely mechanism for C70 fullerenes stabilization in water is surface hydroxylation with covalent attachment of water hydroxyls to C70 fullerene carbons. Raman and infrared absorption spectra of C70FAS showed characteristic vibrational bands of C70 fullerenes with a slight broadening and low-frequency shift of ∼1 cm^−1, indicating the attachment of water hydroxyls to the C70 fullerene carbons. The photoluminescence spectra showed excitonic emission bands of C70 molecules with intensity depending on their content. UV-VIS absorption spectra demonstrate the absorption bands typical for monomeric C70 fullerene. Finally, the dynamic light scattering data confirmed that C70FAS is a typical colloidal fluid containing both individual C70 molecules and their nano aggregates up to 100 nm. These findings provide insights into the stabilization mechanism of C70 fullerenes in water and may have implications for their potential application in nanobiotechnology.



https://doi.org/10.1080/1536383X.2023.2229461
Shin, Dong Wook; Matsukuma, Hiraku; Sato, Ryo; Manske, Eberhard; Gao, Wei
Improved peak-to-peak method for cavity length measurement of a Fabry-Perot etalon using a mode-locked femtosecond laser. - In: Optics express, ISSN 1094-4087, Bd. 31 (2023), 16, S. 25797-25814

Differing from the conventional peak-to-peak method using two neighboring spectral peaks in the frequency-domain fringe spectrum of the spectral response of a Fabry-Perot etalon to a femtosecond laser, which contains N spectral peaks equally spaced with a spacing of the etalon free spectral range (FSR), the proposed method employs a pair of spectral peaks with a spacing of an integer multiple k (k ≫ 1) of FSR for measurement of the etalon cavity length d with a reduced measurement error. Under the constrain of the total N spectral peaks obtainable in the finite spectral range of the femtosecond laser, the optimized k is identified to be N/2 in consideration of an averaging operation using N - k samples of d to achieve the minimum measurement error. The feasibility of the proposed method is demonstrated by experimental results with an uncertainty analysis based on "Guides to the Expression of Uncertainty in Measurement".



https://doi.org/10.1364/OE.493507
Omidian, Maryam; Schulte, Stefan; Néel, Nicolas; Kröger, Jörg
Scanning tunneling spectroscopy of lithium-decorated graphene. - In: Annalen der Physik, ISSN 1521-3889, Bd. 535 (2023), 11, 2300249, S. 1-8

Lithium decoration of graphene on SiC(0001) is achieved in a surface science approach by intercalation and adsorption of the alkali metal. Spectroscopy of the differential conductance with a scanning tunneling microscope at the Li-decorated graphene surfaces does not give rise to a pairing gap at the Fermi energy, which may be expected because of the previously predicted superconducting phase [Profeta et al., Nat. Phys. 2012, 8, 131]. Rather, pronounced gaps in the spectroscopic data of intercalated samples reflect the excitation of graphene phonons. Rationales that possibly explain this discrepancy between experimental findings and theoretical predictions are suggested.



https://doi.org/10.1002/andp.202300249
Ran, Yan; Ren, Jie; Yang, Zhi Chao; Zhao, Huaping; Wang, Yude; Lei, Yong
The 3D flower-like MnV12O31&hahog;10H2O as a high-capacity and long-lifespan cathode material for aqueous zinc-ion batteries. - In: Small structures, ISSN 2688-4062, Bd. 4 (2023), 11, 2300136, S. 1-11

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.



https://doi.org/10.1002/sstr.202300136