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    Plasma-assisted synthesis and high-resolution characterization of anisotropic elemental and bimetallic core-shell magnetic nanoparticles
    (Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2014) Hennes, M.; Lotnyk, A.; Mayr, S.G.
    Magnetically anisotropic as well as magnetic core-shell nanoparticles (CS-NPs) with controllable properties are highly desirable in a broad range of applications. With this background, a setup for the synthesis of heterostructured magnetic core-shell nanoparticles, which relies on (optionally pulsed) DC plasma gas condensation has been developed. We demonstrate the synthesis of elemental nickel nanoparticles with highly tunable sizes and shapes and Ni@Cu CS-NPs with an average shell thickness of 10 nm as determined with scanning electron microscopy, high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy measurements. An analytical model that relies on classical kinetic gas theory is used to describe the deposition of Cu shell atoms on top of existing Ni cores. Its predictive power and possible implications for the growth of heterostructured NP in gas condensation processes are discussed.
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    Role 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, Bernd
    Understanding 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.
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    Morphology, Optical Properties and Photocatalytic Activity of Photo- and Plasma-Deposited Au and Au/Ag Core/Shell Nanoparticles on Titania Layers
    (Basel : MDPI, 2018-7-6) Müller, Alexander; Peglow, Sandra; Karnahl, Michael; Kruth, Angela; Junge, Henrik; Brüser, Volker; Scheu, Christina
    Titania is a promising material for numerous photocatalytic reactions such as water splitting and the degradation of organic compounds (e.g., methanol, phenol). Its catalytic performance can be significantly increased by the addition of co-catalysts. In this study, Au and Au/Ag nanoparticles were deposited onto mesoporous titania thin films using photo-deposition (Au) and magnetron-sputtering (Au and Au/Ag). All samples underwent comprehensive structural characterization by grazing incidence X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Nanoparticle distributions and nanoparticle size distributions were correlated to the deposition methods. Light absorption measurements showed features related to diffuse scattering, the band gap of titania and the local surface plasmon resonance of the noble metal nanoparticles. Further, the photocatalytic activities were measured using methanol as a hole scavenger. All nanoparticle-decorated thin films showed significant performance increases in hydrogen evolution under UV illumination compared to pure titania, with an evolution rate of up to 372 μL H2 h−1 cm−2 representing a promising approximately 12-fold increase compared to pure titania.