Abstract: ''1201'' Tl-based substituted cuprates of the type (Tl1-xMx) Sr2CuO5 have been synthesized for M = Nb, Ta, or W. These materials do not superconduct due to a statistical distribution of some of the M for Cu. The remarkable feature of these materials is the ordering observed between Tl and M in the (Tl1-xMx-epsilon)O plane. The type of ordering depends on the composition and shows remarkable similarities with the ordering in Ni-Mo or other so-called 1 1/2 0 type fcc-based alloys or with the ordering in rocksalt oxides TiOx. The short-range order, for M = W, can be readily interpreted in terms of a mixing of nano-clusters with two different compositions. These observations of two-dimensional ordering confirm recent ideas about ordering in three-dimensional fcc-based alloys.

Abstract: Plasma‐based CO₂conversion has attracted increasing interest. However, to understand the impact of plasma operation on post‐plasma processes, we studied the effect of adding N₂, N₂/CH₄and N₂/CH₄/H₂O to a CO₂gliding arc plasmatron (GAP) to obtain valuable insights into their impact on exhaust stream composition and temperature, which will serve as feed gas and heat for post‐plasma catalysis (PPC). Adding N₂improves the CO₂conversion from 4 % to 13 %, and CH₄addition further promotes it to 44 %, and even to 61 % at lower gas flow rate (6 L/min), allowing a higher yield of CO and hydrogen for PPC. The addition of H₂O, however, reduces the CO₂conversion from 55 % to 22 %, but it also lowers the energy cost, from 5.8 to 3 kJ/L. Regarding the temperature at 4.9 cm post‐plasma, N₂addition increases the temperature, while the CO₂/CH₄ratio has no significant effect on temperature. We also calculated the temperature distribution with computational fluid dynamics simulations. The obtained temperature profiles (both experimental and calculated) show a decreasing trend with distance to the exhaust and provide insights in where to position a PPC bed.

Abstract: Ruddlesden-Popper La????Sr2−????MnO4−???? materials are interesting symmetric solid oxide
fuel cell electrodes due to their good redox stability, mixed ionic and electronic conducting behavior and thermal expansion that matches well with common electrolytes. In reducing environments – as at a solid oxide fuel cell anode – the x = 0.5 member, i.e. La0.5Sr1.5MnO4−????, has a much higher total conductivity than compounds with a different La/Sr ratio, although all those compositions have the same K2NiF4-type I4/mmm structure. The origin for this conductivity difference is not yet known in literature. Now, a combination of in-situ and ex-situ 3D electron diffraction, high-resolution imaging, energy-dispersive X-ray analysis and electron energy-loss spectroscopy uncovered clear differences between x=0.25 and x=0.5 in the pristine structure, as well as in the transformations upon high-temperature reduction. In La0.5Sr1.5MnO4−????, Ruddlesden-Popper n=2 layer defects and an amorphous surface layer are present, but not in La0.25Sr1.75MnO4−????. After annealing at 700°C in 5% H2/Ar, La0.25Sr1.75MnO4−???? transforms to a tetragonal 2D incommensurately modulated structure with modulation vectors ⃗????1 = 0.2848(1) · (⃗????* +⃗????*) and ⃗????2 =0.2848(1) · (⃗????* – ⃗????*), whereas La0.5Sr1.5MnO4−???? only partially transforms to an orthorhombic 1D incommensurately modulated structure,
with ⃗???? = 0.318(2) · ⃗????*. Perovskite domains grow at the crystal edge at 700°C in 5%
H2 or vacuum, due to the higher La concentration on the surface compared to the bulk, which leads to a different thermodynamic equilibrium. Since it is known that a lower degree of oxygen vacancy ordering and a higher amount of perovskite blocks enhance oxygen mobility, those differences in defect structure and structural transformation upon reduction, might all contribute to the higher conductivity of La0.5Sr1.5MnO4−???? in solid oxide fuel cell anode conditions compared to other La/Sr ratios.

Abstract: Solid carbon deposition is a persistent challenge in dry reforming of methane (DRM), affecting both classical and plasma-based processes. In this work, we use a microwave plasma in reverse vortex flow configuration to overcome this issue in CO₂/CH₄plasmas. Indeed, this configuration efficiently mitigates carbon deposition, enabling operation even with pure CH₄feed gas, in contrast to other configurations. At the same time, high reactor performance is achieved, with CO₂and CH₄conversions reaching 33% and 44% respectively, at an energy cost of 14 kJ L⁻¹for a CO₂ : CH₄ratio of 1 : 1. Laser scattering and optical emission imaging demonstrate that the shorter residence time in reverse vortex flow lowers the gas temperature in the discharge, facilitating a shift from full to partial CH₄pyrolysis. This underscores the pivotal role of flow configuration in directing process selectivity, a crucial factor in complex chemistries like CO₂/CH₄mixtures and very important for industrial applications.

Abstract: In this study, the multi-layer self-assembled molecular network formation of an alkylated tetrathiafulvalene compound is studied at the liquid-solid interface between 1-phenyloctane and graphite. A combined theoretical/experimental approach associating force-field and quantum-chemical calculations with scanning tunnelling microscopy is used to determine the two-dimensional self-assembly beyond the monolayer, but also to further the understanding of the molecular adsorption conformation and its impact on the molecular packing within the assemblies at the monolayer and bilayer level.

Abstract: Plasma-based dry reforming of methane (DRM) into
high-value-added oxygenates is an appealing approach to enable
otherwise thermodynamically unfavorable chemical reactions at
ambient pressure and near room temperature. However, it suffers
from coke deposition due to the deep decomposition of CH4. In this
work, we assess the DRM performance upon O2 addition, as well as
varying temperature, CO2/CH4 ratio, discharge power, and gas
residence time, for optimizing oxygenate production. By adding O2,
the main products can be shifted from syngas (CO + H2) toward
oxygenates. Chemical kinetics modeling shows that the improved
oxygenate production is due to the increased concentration of
oxygen-containing radicals, e.g., O, OH, and HO2, formed by electron
impact dissociation [e + O2 → e + O + O/O(1D)] and subsequent
reactions with H atoms. Our study reveals the crucial role of oxygen-coupling in DRM aimed at oxygenates, providing practical
solutions to suppress carbon deposition and at the same time enhance the oxygenates production in plasma-assisted DRM.

Abstract: technologies have been expanding, and one of the most exciting and rapidly growing
applications is in biology and medicine. Most biomedical studies with DBD plasma systems are performed in vitro, which include cells grown on the surface of plastic well plates, or in vivo, which include animal research models (e.g. mice, pigs). Since many DBD systems use the biological target as the secondary electrode for direct plasma generation and treatment, they are sensitive to the surface properties of the target, and thus can be altered based on the in vitro or in vivo system used. This could consequently affect biological response from plasma treatment. Therefore, in this study, we investigated the DBD plasma behavior both in vitro (i.e. 96-well flat bottom plates, 96-well U-bottom plates, and 24-well flat bottom plates), and in vivo (i.e. mouse skin). Intensified charge coupled device (ICCD) imaging was performed and the plasma discharges were visually distinguishable between the different systems. The geometry of the wells did not affect DBD plasma generation for low application distances (≤ 2 mm), but differentially affected plasma uniformity on the bottom of the well at greater distances. Since DBD plasma treatment in vitro is rarely performed in dry wells for plasma medicine experiments, the effect of well wetness was also investigated. In all in vitro cases, the uniformity of the DBD plasma was affected when comparing wet versus dry wells, with the plasma in the wide-bottom wells appearing the most similar to plasma generated on mouse skin. Interestingly, based on quantification of ICCD images, the DBD plasma intensity per surface area demonstrated an exponential one-phase decay with increasing application distance, regardless of the in vitro or in vivo system. This trend is similar to that of the energy per pulse of plasma, which is used to determine the total plasma treatment energy for biological systems. Optical emission spectroscopy performed on the plasma revealed similar trends in radical species generation between the plastic well plates and mouse skin. Therefore, taken together, DBD plasma intensity per surface area may be a valuable parameter to be used as a simple method for in situ monitoring during biological treatment and active plasma treatment control, which can be applied for in vitro and in vivo systems.

Abstract: Plasma-catalytic dry reforming of CH4 (DRM) is promising to convert the greenhouse gasses CH4 and CO2 into value-added chemicals, thus simultaneously providing an alternative to fossil resources as feedstock for the chemical industry. However, while many experiments have been dedicated to plasma-catalytic DRM, there is no consensus yet in literature on the optimal choice of catalyst for targeted products, because the underlying mechanisms are far from understood. Indeed, plasma catalysis is very complex, as it encompasses various chemical and physical interactions between plasma and catalyst, which depend on many parameters. This complexity hampers the comparison of experimental results from different studies, which, in our opinion, is an important bottleneck in the further development of this promising research field. Hence, in this perspective paper, we describe the important physical and chemical effects that should be accounted for when designing plasma-catalytic experiments in general, highlighting the need for standardized experimental setups, as well as careful documentation of packing properties and reaction conditions, to further advance this research field. On the other hand, many parameters also create many windows of opportunity for further optimizing plasma-catalytic systems. Finally, various experiments also reveal the lack of improvement in plasma catalysis compared to plasma-only, specifically for DRM, but the underlying mechanisms are unclear. Therefore, we present our newly developed coupled plasma-surface kinetics model for DRM, to provide more insight in the underlying reasons. Our model illustrates that transition metal catalysts can adversely affect plasmacatalytic DRM, if radicals dominate the plasma-catalyst interactions. Thus, we demonstrate that a good understanding of the plasma-catalyst interactions is crucial to avoiding conditions at which these interactions negatively affect the results, and we provide some recommendations for improvement. For instance, we believe that plasma-catalytic DRM may benefit more from higher reaction temperatures, at which vibrational excitation can enhance the surface reactions.