1. Resolving the dilemma of Fe-N-C catalysts by the selective synthesis of tetrapyrrolic active sites via an imprinting strategyDavide Menga, Jian Liang Low, Yan-Sheng Li, Iztok Arčon, Burak Koyutürk, Friedrich Wagner, Francisco Ruiz-Zepeda, Miran Gaberšček, Beate Paulus, Tim-Patrick Fellinger, 2021, original scientific article Abstract: Combining the abundance and inexpensiveness of
their constituent elements with their atomic dispersion, atomically
dispersed Fe−N−C catalysts represent the most promising
alternative to precious-metal-based materials in proton exchange
membrane (PEM) fuel cells. Due to the high temperatures
involved in their synthesis and the sensitivity of Fe ions toward
carbothermal reduction, current synthetic methods are intrinsically
limited in type and amount of the desired, catalytically active Fe−
N4 sites, and high active site densities have been out of reach
(dilemma of Fe−N−C catalysts). We herein identify a paradigm
change in the synthesis of Fe−N−C catalysts arising from the
developments of other M−N−C single-atom catalysts. Supported
by DFT calculations we propose fundamental principles for the synthesis of M−N−C materials. We further exploit the proposed
principles in a novel synthetic strategy to surpass the dilemma of Fe−N−C catalysts. The selective formation of tetrapyrrolic Zn−N4
sites in a tailor-made Zn−N−C material is utilized as an active-site imprint for the preparation of a corresponding Fe−N−C catalyst.
By successive low- and high-temperature ion exchange reactions, we obtain a phase-pure Fe−N−C catalyst, with a high loading of
atomically dispersed Fe (>3 wt %). Moreover, the catalyst is entirely composed of tetrapyrrolic Fe−N4 sites. The density of
tetrapyrrolic Fe−N4 sites is more than six times as high as for previously reported tetrapyrrolic single-site Fe−N−C fuel cell catalysts
Keywords: Fe-N-C catalysts, selective synthesis, tetrapyrrolic active sites, EXAFS, XANES, single atom, DFT
Published in RUNG: 25.10.2021; Views: 1342; Downloads: 52
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2. The mechanism of Li2S activation in lithium-sulfur batteries: Can we avoid the polysulfide formation?Alen Vižintin, Laurent Chabanne, Elena Tchernychova, Iztok Arčon, Lorenzo Stievano, Giuliana Aquilanti, Markus Antonietti, Tim-Patric Fellinger, Robert Dominko, 2017, original scientific article Abstract: Electrochemical reactions in the LieS batteries are considered as a multistep reaction process with at least
2e3 equilibrium states. Here we report a possibility of having a conversion of Li2S into sulfur without
detectible formation of polysulfides. That was confirmed by using a novel material system consisting of
carbon coated Li2S particles prepared by carbothermal reduction of Li2SO4. Two independent in operando
measurements showed direct oxidation of Li2S into sulfur for this system, with almost negligible formation
of polysulfides at potentials above 2.5 V vs. Li/Liþ. Our results link the diversity of first charge profiles in the
literature to the Li2S oxidation mechanism and show the importance of ionic wiring within the material.
Furthermore, we demonstrate that the Li2S oxidation mechanism depends on the relative amount of
soluble sulfur in the electrolyte. By controlling the type and the amount of electrolyte within the encapsulating
carbon shell, it is thereby possible to control the reaction mechanism of Li2S activation.
Keywords: Lithium-sulfur batteries
Li2S active material
XAS
UV/Vis spectroscopy
Li2S activation
Published in RUNG: 03.03.2017; Views: 4615; Downloads: 0
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