1. 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: ključnih besedah
Keywords: Fe-N-C catalysts, selective synthesis, tetrapyrrolic active sites, EXAFS, XANES, single atom, DFT
Published: 25.10.2021; Views: 1022; Downloads: 44
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2. Insight into the interdependence of Ni and Al in bifunctional Ni/ZSM-5 catalysts at the nanoscaleNataša Novak Tušar, Nataša Zabukovec Logar, Gregor Mali, Janez Volavšek, Simone Pollastri, Goran Dražić, Danilo Oliveira de Souza, Iztok Arčon, Hue-Tong Vu, 2022, original scientific article Abstract: Catalyst design is crucial for improving catalytic activity and product selectivity. In a bifunctional Ni/ZSM-5
zeolite type catalyst, catalytic properties are usually tuned via varying Al and Ni contents. While changes in
acid properties associated with Al sites are usually closely investigated, Ni phases, however, receive
inadequate attention. Herein, we present a systematic structural study of Ni in the Ni/ZSM-5 materials by
using Ni K-edge XANES and EXAFS analyses, complemented by XRD and TEM, to resolve the changes in
the local environment of Ni species induced by the different Al contents of the parent ZSM-5 prepared
by a “green”, template free technique. Ni species in Ni/ZSM-5 exist as NiO crystals (3–50 nm) and as
charge compensating Ni2+ cations. The Ni K-edge XANES and EXAFS results enabled the quantification
of Ni-containing species. At a low Al to Si ratio (nAl/nSi # 0.04), the NiO nanoparticles predominate in
the samples and account for over 65% of Ni phases. However, NiO is outnumbered by Ni2+ cations
attached to the zeolite framework in ZSM-5 with a high Al to Si ratio (nAl/nSi ¼ 0.05) due to a higher
number of framework negative charges imparted by Al. The obtained results show that the number of
highly reducible and active NiO crystals is strongly correlated with the framework Al sites present in
ZSM-5 zeolites, which depend greatly on the synthesis conditions. Therefore, this kind of study is
beneficial for any further investigation of the catalytic activities of Ni/ZSM-5 and other metal-modified
bifunctional catalysts.
Found in: ključnih besedah
Keywords: Ni/ZSM-5 catalysts, zeolite, Ni XANES, EXAFS
Published: 11.05.2022; Views: 663; Downloads: 28
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3. Monitoring chemical processes on the atomic scale in catalysts by operando X-ray absorption spectrometryIztok Arčon, 2022, published scientific conference contribution abstract (invited lecture) Abstract: X-ray absorption spectroscopy (XAS) is a powerful tool for characterisation of local structure and chemical state of selected elements in different new functional materials and biological or environmental samples. The rapid development of extremely bright synchrotron sources of X-ray and ultraviolet light in recent years has opened new possibilities for research of matter at the atomic or molecular level, indispensable in the development of new functional nanostructured materials with desired properties. The lecture will present the possibilities offered by X-ray absorption spectroscopy with synchrotron light for ex-situ and in-situ or operando characterization of various catalyst materials before, after and during their operation. With the operando XANES and EXAFS methods it is possible to track changes in the valence states and local structures of selected elements in various (photo)catalysts, during chemical reactions under controlled reaction conditions, thus gaining insight into the dynamic functional properties and reaction mechanisms of these materials. New synchrotron light sources also opened the possibility of combining X-ray absorption or emission spectroscopy and microscopy with a resolution of up to a few tens of nanometres, allowing micro-XAS analysis with high spatial resolution.
Found in: ključnih besedah
Keywords: XAS, operando XANES, EXAFS, catalysts
Published: 01.06.2022; Views: 497; Downloads: 0
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4. Monitoring chemical processes in (photo)catalysts and energy storage materials by operando X-ray absorption spectroscopyIztok Arčon, 2022, published scientific conference contribution abstract (invited lecture) Abstract: X-ray absorption spectroscopy (XAS) is a powerful tool for characterisation of local structure and chemical state of selected elements in different new functional materials and biological or environmental samples. The XAS spectroscopy is based on extremely bright synchrotron radiation X-rays sources, which allow precise characterisation of bulk, nanostructured or highly diluted samples. The rapid development of extremely bright synchrotron sources of X-ray and ultraviolet light in recent years has opened new possibilities for research of matter at the atomic or molecular level, indispensable in the development of new functional nanostructured materials with desired properties. The talk will present the possibilities offered by X-ray absorption spectroscopy with synchrotron light for ex-situ or operando characterization of various functional porous and other nanomaterials, before, after and during their operation [1,2,3,4]. New generation of synchrotron light sources also opened the possibility of combining X-ray absorption with high-resolution emission [5] and inelastic scattering spectroscopy [6], and microscopy with sub-micron resolution [7]. Examples of operando XANES and EXAFS analysis to track changes in the valence states and local structures of selected elements in different energy storage materials and in various (photo)catalysts, during chemical reactions under controlled reaction conditions, will be presented, which provided insight into the dynamic functional properties and reaction mechanisms of these materials. Access to SR facilities of Petra III (beamlines P65, P64 and P01), ESRF (beamlines BM23, ID21, ID26) and Elettra (beamlines XAFS, XRF), for the presented research is kindly acknowledged.
Found in: ključnih besedah
Keywords: X-ray absorption spectroscopy, operando XANES, EXAFS, catalysts, batteries
Published: 07.10.2022; Views: 253; Downloads: 0
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