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- ItemRole of Reaction Intermediate Diffusion on the Performance of Platinum Electrodes in Solid Acid Fuel Cells(Basel : MDPI, 2021) Lorenz, Oliver; Kühne, Alexander; Rudolph, Martin; Diyatmika, Wahyu; Prager, Andrea; Gerlach, Jürgen W.; Griebel, Jan; Winkler, Sara; Lotnyk, Andriy; Anders, André; Abel, BerndUnderstanding the reaction pathways for the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR) is the key to design electrodes for solid acid fuel cells (SAFCs). In general, electrochemical reactions of a fuel cell are considered to occur at the triple-phase boundary where an electrocatalyst, electrolyte and gas phase are in contact. In this concept, diffusion processes of reaction intermediates from the catalyst to the electrolyte remain unconsidered. Here, we unravel the reaction pathways for open-structured Pt electrodes with various electrode thicknesses from 15 to 240 nm. These electrodes are characterized by a triple-phase boundary length and a thickness-depending double-phase boundary area. We reveal that the double-phase boundary is the active catalytic interface for the HOR. For Pt layers ≤ 60 nm, the HOR rate is rate-limited by the processes at the gas/catalyst and/or the catalyst/electrolyte interface while the hydrogen surface diffusion step is fast. For thicker layers (>60 nm), the diffusion of reaction intermediates on the surface of Pt be-comes the limiting process. For the ORR, the predominant reaction pathway is via the triple-phase boundary. The double-phase boundary contributes additionally with a diffusion length of a few nanometers. Based on our results, we propose that the molecular reaction mechanism at the electrode interfaces based upon the triple-phase boundary concept may need to be extended to an effective area near the triple-phase boundary length to include all catalytically relevant diffusion processes of the reaction intermediates. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.
- ItemCompositional Patterning in Carbon Implanted Titania Nanotubes(Weinheim : Wiley-VCH, 2021) Kupferer, Astrid; Holm, Alexander; Lotnyk, Andriy; Mändl, Stephan; Mayr, Stefan G.Ranging from novel solar cells to smart biosensors, titania nanotube arrays constitute a highly functional material for various applications. A promising route to modify material characteristics while preserving the amorphous nanotube structure is present when applying low-energy ion implantation. In this study, the interplay of phenomenological effects observed upon implantation of low fluences in the unique 3D structure is reported: sputtering versus readsorption and plastic flow, amorphization versus crystallization and compositional patterning. Patterning within the oxygen and carbon subsystem is revealed using transmission electron microscopy. By applying a Cahn–Hilliard approach within the framework of driven alloys, characteristic length scales are derived and it is demonstrated that compositional patterning is expected on free enthalpy grounds, as predicted by density functional theory based ab initio calculations. Hence, an attractive material with increased conductivity for advanced devices is provided. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH
- ItemRoom temperature synthesis of an amorphous MoS2 based composite stabilized by N-donor ligands and its light-driven photocatalytic hydrogen production(London : RSC Publishing, 2015) Niefind, Felix; Djamil, John; Bensch, Wolfgang; Srinivasan, Bikshandarkoil R.; Sinev, Ilya; Grünert, Wolfgang; Deng, Mao; Kienle, Lorenz; Lotnyk, Andriy; Mesch, Maria B.; Senker, Jürgen; Dura, Laura; Beweries, TorstenHerein an entirely new and simple room temperature synthesis of an amorphous molybdenum sulfide stabilized by complexing ammonia and hydrazine is reported. The resulting material exhibits an outstanding activity for the photocatalytic hydrogen evolution driven by visible light. It is chemically stable during the reaction conditions of the photocatalysis and shows unusual thermal stability up to 350 °C without crystallization. The new material is obtained by a reaction of solid ammonium tetrathiomolybdate and gaseous hydrazine. In the as-prepared state Mo atoms are surrounded by μ2-briding S2−, NH3 and hydrazine, the latter being coordinated to Mo(IV) in a bridging or side-on mode. Heating at 450 °C or irradiation with an electron beam generates nanosized crystalline MoS2 slabs. The two modes for crystallization are characterized by distinct mechanisms for crystal growth. The stacking of the slabs is low and the material exhibits a pronounced turbostratic disorder. Heat treatment at 900 °C yields more ordered MoS2 but structural disorder is still present. The visible-light driven hydrogen evolution experiments evidence an outstanding performance of the as-prepared sample. The materials were thoroughly characterized by optical spectroscopy, chemical analysis, in situ HRTEM, XRD, 1H and 15N solid-state NMR, XPS, and thermal analysis.
- ItemStrongly enhanced and tunable photovoltaic effect in ferroelectric-paraelectric superlattices(Washington, DC [u.a.] : Assoc., 2021) Yun, Yeseul; Mühlenbein, Lutz; Knoche, David S.; Lotnyk, Andriy; Bhatnagar, AkashEver since the first observation of a photovoltaic effect in ferroelectric BaTiO3, studies have been devoted to analyze this effect, but only a few attempted to engineer an enhancement. In conjunction, the steep progress in thin-film fabrication has opened up a plethora of previously unexplored avenues to tune and enhance material properties via growth in the form of superlattices. In this work, we present a strategy wherein sandwiching a ferroelectric BaTiO3 in between paraelectric SrTiO3 and CaTiO3 in a superlattice form results in a strong and tunable enhancement in photocurrent. Comparison with BaTiO3 of similar thickness shows the photocurrent in the superlattice is 103 times higher, despite a nearly two-thirds reduction in the volume of BaTiO3. The enhancement can be tuned by the periodicity of the superlattice, and persists under 1.5 AM irradiation. Systematic investigations highlight the critical role of large dielectric permittivity and lowered bandgap.