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1.
Performance of copper - based catalysts for electrochemical CO2 reduction
Stefan Popović, 2023, doctoral dissertation

Abstract: The industrial era has brought a never-ending problem to civilization through the emission of greenhouse gases (GHGs) while extracting energy from fossil fuels for a variety of processes. Among different GHGs, carbon dioxide (CO2) stood out as one of the most impactful and dangerous gases causing climatic disasters around the globe. However, CO2 as the abundant C1 building block, through the conversion pathways gives a plethora of opportunities to convert it into a wide range of commercial products and applications. The holistic approach among different conversion pathways is the electrochemical reduction of CO2 (eCO2R), ideally powered by renewable energy from intermittent sources such as wind and solar power. A silver bullet of the process is to find a catalyst that is active, selective, and stable. Copper has been recognized as the only monometallic catalyst that can produce products that require a transfer of >2e-. However, in recent years the increased awareness of its reconstructive nature under eCO2RR-relevant conditions multiplied the complexity of the parameters that can influence the reaction. Therefore overall thesis's approach to studying copper-based catalysts is based to understand the reconstructive aspect and the stability of Cu-based catalysts, and deeply comprehend their relationship with the activity/selectivity. Chapter 1 gives an introduction to the recent activities in the field of carbon capture, utilization and storage (CCSU) technologies, the fundaments of CO2 as a molecule, and its pathway toward state-of-the-art discoveries in the eCO2 R reaction. Afterward, the thesis focuses on the main experimental technique to produce nanostructured copper-based materials, namely, electrodeposition (Chapter 2). A big part of the thesis focuses on the establishment of an electrochemical setup for activity/selectivity measu rement. The setup consists of two parts: 1) construction of the custom-made gas-tight sandwich-type electrochemical cell and 2) optimization of the online gas and ex-situ liquid product detection. After the establishment of the reliable electrochemical setup, Chapter 3 focuses on electrochemically -grown Cu2O nanocubes catalyst and how the reconstructive nature induced by a particular electrochemical protocol influences on boost in activity/selectivity for methane production. The last part of the thesis consists contribution to the fundamental understanding of the degradation mechanisms and stability of Cu -based catalysts under eCO2RR conditions. A unique ex-situ approach, mirrored in identical location scanning electron microscopy (IL-SEM) method is employed to study electrodeposited spherical half-micron particles on the glassy carbon rotating disk electrode (GC-RDE). With this evidence, we could interpret the observed structural changes as two separate electrochemical processes occurring one after another, namely copper dissolution from pre-oxidized native nanoparticles and subsequent (electro -) redeposition of the dissolved copper species in a form of n ew smaller Cu fragments.
Keywords: electrocatalysts, electrochemical CO2 reduction, copper nanoparticles, IL-SEM, stability, degradation
Published in RUNG: 14.11.2023; Views: 636; Downloads: 11
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2.
Winning combination of Cu and Fe oxide clusters with an alumina support for low-temperature catalytic oxidation of volatile organic compounds
Tadej Žumbar, Iztok Arčon, Petar Djinović, Giuliana Aquilanti, Gregor Žerjav, Albin Pintar, Alenka Ristić, Goran Dražić, Janez Volavšek, Gregor Mali, Margarita Popova, Nataša Zabukovec Logar, Nataša Novak Tušar, 2023, original scientific article

Abstract: A γ-alumina support functionalized with transition metals is one of the most widely used industrial catalysts for the total oxidation of volatile organic compounds (VOCs) as air pollutants at higher temperatures (280−450 °C). By rational design of a bimetal CuFe-γ-alumina catalyst, synthesized from a dawsonite alumina precursor, the activity in total oxidation of toluene as a model VOC at a lower temperature (200−380 °C) is achieved. A fundamental understanding of the catalyst and the reaction mechanism is elucidated by advanced microscopic and spectroscopic characterizations as well as by temperature-programmed surface techniques. The nature of the metal−support bonding and the optimal abundance between Cu−O−Al and Fe−O−Al species in the catalysts leads to synergistic catalytic activity promoted by small amounts of iron (Fe/Al = 0.005). The change in the metal oxide−cluster alumina interface is related to the nature of the surfaces to which the Cu atoms attach. In the most active catalyst, the CuO6 octahedra are attached to 4 Al atoms, while in the less active catalyst, they are attached to only 3 Al atoms. The oxidation of toluene occurs via the Langmuir−Hinshelwood mechanism. The presented material introduces a prospective family of low-cost and scalable oxidation catalysts with superior efficiency at lower temperatures.
Keywords: Iron oxide clusters, copper oxide clusters, alumina support, synergistic effect, low-temperature total catalytic oxidation, toluene, Cu, Fe XANES, EXAFS
Published in RUNG: 06.07.2023; Views: 958; Downloads: 11
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Copper bioavailability and leaching in conventional and organic viticulture under environmental stress
Erika Jež, Elisa Pellegrini, Marco Contin, 2023, original scientific article

Abstract: The continuous use of Cu-based fungicides in viticulture has caused Cu accumulation in soils, which represents a major environmental and toxicological concern. The purpose of this study was to verify whether the organic management would be more resilient to temperature and moisture stresses in comparison to conventional practices. Two organic and two conventional vineyard soils, contrasting in pH, were exposed for six months to temperature stress (29 °C), moisture stress (10% water holding capacity—WHC), and combined stresses (29 °C—10% WHC). Main soil properties, Cu speciation, bioavailability, and leaching were monitored before and after 6 months’ incubation. Results confirm that the increase of temperature caused a decrease in both total organic carbon (TOC) and dissolved organic carbon (DOC) (up to 19% and 49%, respectively), a decrease in available ammonium, and an increase in nitrate. Moisture stress tends to mitigate some of these changes. Despite that, changes of Cu bioavailability and leaching were limited and rarely significant. Moreover, no regular trends between conventional and organic management could be observed. Changes in soil pH and total N (TN) appeared as the most influencing properties to regulate Cu behavior in vineyard soils. Calcareous soils were more resistant to environmental stresses compared to acid soils, regardless of the type of management (conventional or organic).
Keywords: soil copper, climate changes, soil organic matter, organic viticulture, BCR speciation
Published in RUNG: 22.02.2023; Views: 1043; Downloads: 17
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5.
Dynamical interplay between the human high-affinity copper transporter hCtr1 and its cognate metal ion
Gulshan Walke , Jana Aupič, Hadeel Kashoua , Pavel Janoš, Shelly Meron , Yulia Shenberger , Zena Qasem , Lada Gevorkyan-Airapetov , Alessandra Magistrato, Sharon Ruthstein , 2022, original scientific article

Abstract: Abnormal cellular copper levels have been clearly implicated in genetic diseases, cancer, and neurodegeneration. Ctr1, a high-affinity copper transporter, is a homotrimeric integral membrane protein that provides the main route for cellular copper uptake. Together with a sophisticated copper transport system, Ctr1 regulates Cu(I) metabolism in eukaryotes. Despite its pivotal role in normal cell function, the molecular mechanism of copper uptake and transport via Ctr1 remains elusive. In this study, electron paramagnetic resonance (EPR), UV-visible spectroscopy, and all-atom simulations were employed to explore Cu(I) binding to full-length human Ctr1 (hCtr1), thereby elucidating how metal binding at multiple distinct sites affects the hCtr1 conformational dynamics. We demonstrate that each hCtr1 monomer binds up to five Cu(I) ions and that progressive Cu(I) binding triggers a marked structural rearrangement in the hCtr1 C-terminal region. The observed Cu(I)-induced conformational remodeling suggests that the C-terminal region may play a dual role, serving both as a channel gate and as a shuttle mediating the delivery of copper ions from the extracellular hCtr1 selectivity filter to intracellular metallochaperones. Our findings thus contribute to a more complete understanding of the mechanism of hCtr1-mediated Cu(I) uptake and provide a conceptual basis for developing mechanism-based therapeutics for treating pathological conditions linked to de-regulated copper metabolism.
Keywords: ctr1, copper, epr, molecular dynamics
Published in RUNG: 15.09.2022; Views: 1065; Downloads: 0
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6.
The conformational plasticity of the selectivity filter methionines controls the in-cell Cu(I) uptake through the CTR1 transporter
Pavel Janoš, Jana Aupič, Sharon Ruthstein , Alessandra Magistrato, 2022, original scientific article

Abstract: Copper is a trace element vital to many cellular functions. Yet its abnormal levels are toxic to cells, provoking a variety of severe diseases. The high affinity copper transporter 1 (CTR1), being the main in-cell copper [Cu(I)] entry route, tightly regulates its cellular uptake via a still elusive mechanism. Here, all-atoms simulations unlock the molecular terms of Cu(I) transport in eukaryotes disclosing that the two methionine (Met) triads, forming the selectivity filter, play an unprecedented dual role both enabling selective Cu(I) transport and regulating its uptake rate thanks to an intimate coupling between the conformational plasticity of their bulky side chains and the number of bound Cu(I) ions. Namely, the Met residues act as a gate reducing the Cu(I) import rate when two ions simultaneously bind to CTR1. This may represent an elegant autoregulatory mechanism through which CTR1 protects the cells from excessively high, and hence toxic, in-cell Cu(I) levels. Overall, our outcomes resolve fundamental questions in CTR1 biology and open new windows of opportunity to tackle diseases associated with an imbalanced copper uptake.
Keywords: copper, membrane transporter, molecular dynamics, QM/MM, free energy
Published in RUNG: 15.09.2022; Views: 1275; Downloads: 0
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Effect of Na, Cs and Ca on propylene epoxidation selectivity over CuOx/SiO2 catalysts studied by catalytic tests, in-situ XAS and DFT
Janvit Teržan, Matej Huš, Iztok Arčon, Blaž Likozar, Petar Djinović, 2020, original scientific article

Abstract: This research focuses on epoxidation of propylene over pristine, Na, Ca and Cs modified CuOx/SiO2 catalysts using O2. The selectivity of the reaction is analyzed using a combination of catalytic tests, in-situ XAS and DFT calculations. The initially present subnanometer CuO clusters are present in all catalysts which re-disperse/flatten during reaction. During catalytic reaction, the Cu1+ becomes the predominant oxidation state. There is no correlation between propylene oxide (PO) selectivity and copper oxidation state. DFT analysis of the propylene reaction pathway revealed that Na, Cs, and Ca addition decreases the bonding strength of propylene to CuO and decreases the O2 activation barrier, while simultaneously increase the exothermicity of O2 dissociation. The Na induced Cu-O bond modification decreases the activation barrier from 0.87 to 0.71 eV for the oxametallacycle (OMC) ring closure (first step in the reaction pathway favoring selectivity towards PO) compared to pristine 5Cu catalyst. At the same time, we observed an increase (from 0.45 to 0.72 eV) of the barrier for the abstraction of allylic hydrogen. The opposite effect is achieved by Ca addition: the activation barrier for OMC ring closure increases to 1.08 eV and that for allylic hydrogen stripping decreases to 0.16 eV.
Keywords: Alkali modification, propylene epoxidation, reaction mechanism, copper oxide, activation barrier.
Published in RUNG: 05.06.2020; Views: 2707; Downloads: 0
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9.
Copper tolerance strategies involving the root cell wall pectins in Silene paradoxa L.
Ilaria Colzi, Miluscia Arnetoli, Alessia Gallo, Saer Doumett, Massimo Del Bubba, Sara Pignattelli, Roberto Gabbrielli, Cristina Gonnelli, 2012, original scientific article

Abstract: New insights were provided on the function of root cell wall pectin concentration and methylation degree in copper tolerance studying contrasting ecotypes of Silene paradoxa. A metallicolous copper tolerant population and a non-metallicolous sensitive population were grown in hydroponics and exposed to different CuSO4 treatments to evaluate copper accumulation in relation to pectin concentration and methylation degree of the root cell wall. In short-term exposure experiments the tolerant population decreased root cell wall pectin concentration and increased their methylation degree, while the sensitive population did not respond. Moreover, a positive correlation between root pectin concentration and metal accumulation in root apoplast and symplast was found. In addition, a negative correlation between pectin methylation degree and apoplastic copper concentration were found to be negatively correlated. In longterm exposure experiments, the sensitive population increased the concentration of pectins with the same methylation degree and consequently the ability of its root cell wall to bind the metal. The opposite phenomenon was shown by the tolerant population. Moreover, pectin methylation degree was higher in the tolerant population in respect to the sensitive one, possibly to limit metal binding to the root cell wall. Therefore, in the copper tolerant population of S. paradoxa the generation of metal-excluding root cell walls was suggested to be one of the factors concurring to guarantee a low apoplastic copper accumulation and probably also to limit symplastic copper uptake by the root cells.
Keywords: Copper tolerance Cell wall Pectin Methylation Root
Published in RUNG: 20.04.2020; Views: 2724; Downloads: 0
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10.
A multielement analysis of Cu induced changes in the mineral profilesof Cu sensitive and tolerant populations of Silene paradoxa L.
Sara Pignattelli, Ilaria Colzi, Antonella Buccianti, Ilenia Cattani, Gian Maria Beone, Henk Schat, Cristina Gonnelli, 2013, original scientific article

Abstract: tThis work investigates the Cu induced changes in element profiles in contrasting ecotypes of Silene para-doxa L. A metallicolous copper tolerant population and a non-metallicolous sensitive population weregrown in hydroponics and exposed to different CuSO4treatments. Shoot and root concentrations of Ca,Cu, Fe, K, Mg, Mn, Mo, Na, P, S and Zn were evaluated through ICP-OES.Results indicated that increasing the environmental Cu concentration had a population dependenteffect on element profiles, shoot-to-root ratios and correlations among the elements. Generally, in thetolerant population Cu treatment induced a higher element accumulation in roots and had minimaleffects on the shoot element profile, thus resulting in a progressively decreasing shoot-to-root ratio foreach element. In the sensitive population element concentrations in root and shoot were much moreaffected and without a consistent trend. Copper treatment also affected the correlations between theelements, both in roots and shoots of the two populations, but more so in the sensitive population thanin the tolerant one. Thus, Cu exposure strongly disturbed element homeostasis in the sensitive population,but barely or not in the tolerant one, probably mainly due to a higher capacity to maintain proper rootfunctioning under Cu exposure in the latter. Differences in element profiles were also observed in theabsence of toxic Cu exposure. These differences may reflect divergent population-specific adaptations todifferential nutrient availability levels prevailing in the populations’ natural environments. There is noevidence of inherent side-effects of the Cu tolerance mechanism operating in the tolerant population.
Keywords: Mineral profile, Copper tolerance, Silene paradoxa, Compositional data analysis
Published in RUNG: 20.04.2020; Views: 2770; Downloads: 0
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