1. Atomically resolved dealloying of structurally ordered Pt nanoalloy as an oxygen reduction reaction electrocatalystAndraž Pavlišič, Primož Jovanovič, Vid Simon Šelih, Martin Šala, Marjan Bele, Goran Dražić, Iztok Arčon, Samo B. Hočevar, Anton Kokalj, Nejc Hodnik, Miran Gaberšček, original scientific article Abstract: The positive effect of intermetallic ordering of platinum alloy nanoparticles on oxygen reduction reaction (ORR) activity has been well established. What is still missing is an understanding of selective leaching of the less noble metal from the ordered structure and its correlation to longterm ORR performance. Using a combination of kinetic Monte Carlo simulations and advanced characterization techniques, we provide unprecedented insight into dealloying of intermetallic PtCu3 nanoparticles a well-known binary alloy. Comparison of ordered and disordered samples with identical initial compositions and particle size distributions reveals an unexpected correlation: whereas the copper dealloying rates in the ordered and disordered counterparts are almost the same, in the ordered structure Pt atoms are surrounded by 15−30% more Cu atoms throughout all the stages of acid leaching. This more convenient Pt−Cu coordination explains the statistically significant increase of 23−37% in ORR activity of the ordered structure at all stages of alloy degradation.
Found in: osebi
Keywords: ORR activity, fuel cells, platinum alloy, nanoparticle stability, intermetallic ordering, kinetic Monte Carlo, dealloying, in situ ICP-MS
Published: 27.09.2016; Views: 3193; Downloads: 0
 Fulltext (3,27 MB) |
2. Electrochemical dissolution of iridium and iridium oxide particles in acidic mediaMiran Gaberšček, Samo B. Hočevar, Vid Simon Šelih, Martin Šala, Marjan Bele, Milena Zorko, Barbara Jozinović, Iztok Arčon, Francisco Ruiz-Zepeda, Nejc Hodnik, Primož Jovanovič, 2017, original scientific article Abstract: Iridium based particles as the most promising proton exchange membrane electrolyser electrocatalysts were investigated
by transmission electron microscopy (TEM), and by coupling of electrochemical flow cell (EFC) with online inductively
coupled plasma mass spectrometer (ICP-MS). Additionally, a thin-film rotating disc electrode (RDE), an identical location transmission
and scanning electron microscopy (IL-TEM and IL-SEM) as well as an X-ray absorption spectroscopy (XAS) studies have
been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that iridium
particles dissolved already well below oxygen evolution reaction (OER) potentials, presumably induced by iridium surface oxidation
and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile type IrO2 particles (T-IrO2)
are substantially more stable and less active in comparison to as prepared metallic (A-Ir) and electrochemically pretreated (E-Ir)
analogues. Interestingly, under OER relevant conditions E-Ir particles exhibit superior stability and activity owing to the altered
corrosion mechanism where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance,
electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low temperature
electrochemical hydrogen production device, namely a proton exchange membrane electrolyser.
Found in: osebi
Keywords: Iridium Oxide Par-ticles, Electrochemical Dissolution of Iridium, Ir L3-edge XANES
Published: 23.08.2017; Views: 2066; Downloads: 0
Fulltext (1,43 MB) |
3. Ceramic synthesis of disordered lithium rich oxyfluoride materialsJean-Marcel Ateba Mba, Iztok Arčon, Gregor Mali, Elena Tchernychova, Ralf Witte, Robert Kruk, Miran Gaberšček, Robert Dominko, 2020, original scientific article Abstract: Disordered lithium-rich transition metal oxyfluorides with a general formula Li1þxMO2Fx (M being a transition
metal) are gaining more attention due to their high specific capacity which can be delivered from the facecentered
cubic (fcc) structure. The most common synthesis procedure involves use of mechanosynthesis. In
this work, ceramic synthesis of lithium rich iron oxyfluoride and lithium rich titanium oxyfluoride are reported.
Two ceramic synthesis routes are developed each leading to the different level of doping with Li and F and
different levels of cationic disorder in the structure. Three different Li1þxMO2Fx samples (x ¼ 0.25, 0.3 and 1) are
compared with a sample prepared by mechanochemical synthesis and non-doped LiFeO2 with fcc structure. The
obtained lithium rich iron oxyfluoride are characterized by use of M€ossbauer spectroscopy, X-ray absorption
spectroscopy, NMR and TEM. Successful incorporation of Li and F have been confirmed and specific capacity that
can be obtained from the samples is in the correlation with the level of disorder introduced with doping,
nevertheless oxidation state of iron in all samples is very similar. Conclusions obtained from lithium rich iron
oxyfluoride are validated by lithium rich titanium oxyfluoride.
Found in: osebi
Keywords: Lithium batteries
Face centered-cubic
Oxyfluoride
Li-rich
Disorder
Published: 05.06.2020; Views: 1040; Downloads: 0
Fulltext (2,37 MB) |
4. Resolving the dilemma of Fe-N-C catalysts by the selective synthesis of tetrapyrrolic active sites via an imprinting strategyTim-Patrick Fellinger, Beate Paulus, Miran Gaberšček, Francisco Ruiz-Zepeda, Friedrich Wagner, Burak Koyutürk, Iztok Arčon, Yan-Sheng Li, Jian Liang Low, Davide Menga, 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
Found in: osebi
Keywords: Fe-N-C catalysts, selective synthesis, tetrapyrrolic active sites, EXAFS, XANES, single atom, DFT
Published: 25.10.2021; Views: 16; Downloads: 0
 Fulltext (0,00 KB)
This document has many files! More...
|
