Abstract: Al-Zn-Mg-based high strength alloys are widely used in aerospace applications due to their low density and excellent mechanical properties. A systematic study of the structural evolution of the nano-precipitation phase and its growth mechanism is an important guide for the design of new high-strength alloys. In this work, the Laves structure precipitates in Al-Zn-Mg(-Cu/Y) alloy was systematically characterized. Based on the structure evolution, the structure of submicron Laves particles and quasicrystalline particles in the alloy at microscale, as well as the regulation of the precipitation behavior after adding Y at nanoscale were further investigated. The main innovative results are summarized as follows: (1) Investigation on coexistence of defect structures in Laves structural nanoprecipitates. Three types of Laves structures can coexist within the η-MgZn2 precipitates: C14, C15 and C36, and the Laves structure transition sequence of C14→C36→C15 in this system was determined. Meanwhile, it was found that there are diverse defect structures in the MgZn2 phase, including stacking faults, planar defects and five-fold domain structures, which have significant effects on relieving the internal stress/strain of the precipitates. (2) Investigation on multiple phase transition of Laves structural nanoprecipitates from C14 to C36 and from C14 to quasicrystal clusters. It is found that C14 precipitates can be completely transformed into the C36 precipitates. And it is also found that the C14 Laves phase structure can also transform into quasicrystalline clusters. These investigations on various phase transition mechanisms among Laves phases provide theoretical support for the microstructural characterization of materials containing multi-scale Laves phases. (3) Characterization of Laves and quasicrystal structural particles in submicron scale. Submicron-scale quasicrystal particles were obtained in conventional casting Al-Zn-Mg-Cu alloys for the first time. Industrial impurity elements Fe and Ni can induce the formation of quasicrystalline particles. When there is no Fe/Ni enriched in particles, the structure is characterized as C15-Laves phase. When Fe/Ni is as quasicrystalline core, a stable core-shell quasicrystalline structure with Al-Fe-Ni nucleus and Mg-Cu-Zn shell can be formed. (4) Investigation on the regulation of nanoscale Laves precipitates’ growth. To regulate the defect structure of the precipitates, rare earth element Y was added in Al-Zn-Mg alloys and its influence on the precipitation behavior was investigated. The addition of Y element can dynamically combine with different alloying elements during aging process, which can refine the size of precipitate and further improve the nucleation rate and precipitation rate of the precipitates.

Abstract: Research efforts on the description of the low-temperature magnetic order and electronic properties of U3O8 have been inconclusive so far. Reinterpreting neutron scattering results, we use group representation theory to show that the ground state presents collinear out-of-plane magnetic moments, with antiferromagnetic coupling both in-layer and between layers. Charge order relieves the initial geometric frustration, generating a slightly distorted honeycomb sublattice with Néel-type order. The precise knowledge of the characteristics of this magnetic ground state is then used to explain the fine features of the band gap. In this system, spin-orbit coupling (SOC) is of critical importance, as it strongly affects the electronic structure, narrowing the gap by ∼38%, compared to calculations neglecting SOC. The predicted electronic structure actually explains the salient features of recent optical absorption measurements, further demonstrating the excellent agreement between the calculated ground state properties and experiment.

Abstract: Matrix assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI) has become a powerful method to extract spatially resolved chemical information in complex materials. This study provides the first use of MALDI-MSI to define spatial–temporal changes in oil paints. Due to the highly heterogeneous nature of oil paints, the sample preparation had to be optimized to prevent molecules from delocalizing. Here, we present a new protocol for the layer-specific analysis of oil paint cross sections achieving a lateral resolution of 10 μm and without losing ionization efficiency due to topographic effects. The efficacy of this method was investigated in oil paint samples containing a mixture of two historic organic pigments, geranium lake and lead white, a mixture often employed in the work of painter Vincent Van Gogh. This methodology not only allows for spatial visualization of the molecules responsible for the pink hue of the paint but also helps to elucidate the chemical changes behind the discoloration of paintings with this composition. The results demonstrate that this approach provides valuable molecular compositional information about the degradation pathways of pigments in specific paint layers and their interaction with the binding medium and other paint components and with light over time. Since a spatial correlation between molecular species and the visual pattern of the discoloration pattern can be made, we expect that mass spectrometry imaging will become highly relevant in future degradation studies of many more historical pigments and paints.

Abstract: Thermally induced oxygen release is an intrinsic structural instability in layered cathodes, which causes thermal runaway issues and becomes increasingly critical with the continuous improvement in energy density. Furthermore, thermal runaway events always occur in electrochemically aged cathodes, where the coupling of the thermal and electrochemical effect remains elusive. Herein, we report the anomalous segregation of cobalt metal in an aged LiCoO2 cathode, which is attributed to the local exposure of the high-energy (100) surface of LiCoO2 and weak interface Co-O dangling bonds significantly promoting the diffusion of Co. The presence of the LCO-Co interface severely aggregated the oxygen release in the form of dramatic Co growth. A unique particle-to-particle oxygen release pathway was also found, starting from the isolated high reduction areas induced by the cycling heterogeneity. This study provides atomistic insight into the robust coupling between the intrinsic structural instability and electrochemical cycling.

Abstract: Carbon dioxide electrochemical reduction (CO2ER) has attracted considerable attention as a technology to recycle CO2 into raw materials for chemicals using renewable energies. We recently found that Zn-Al layered double hydroxides (Zn-Al LDH) have the CO-forming CO2ER activity. However, the activity was only evaluated by using the liquid-phase CO2ER. In this study, Ni-Al and Ni-Fe LDHs as well as Zn-Al LDH were synthesized using a facile coprecipitation process and the gas-phase CO2ER with the LDH-loaded gas-diffusion electrode (GDE) was examined. The products were characterized by XRD, STEM-EDX, BF-TEM and ATR-IR spectroscopy. In the ATR-IR results, the interaction of CO2 with Zn-Al LDH showed a different carbonates evolution with respect to other LDHs, suggesting a different electrocatalytic activity. The LDH-loaded GDE was prepared by simple drop-casting of a catalyst ink onto carbon paper. For gas-phase CO2ER, only Zn-Al LDH exhibited the CO2ER activity for carbon monoxide (CO) formation. By using different potassium salt electrolytes affording neutral to strongly basic conditions, such as KCl, KHCO3 and KOH, the gas-phase CO2ER with Zn-Al LDH-loaded GDE showed 1.3 to 2.1 times higher partial current density for CO formation than the liquid-phase CO2ER.

Abstract: The coupling of methane pyrolysis with the gasification of a solid carbon byproduct provides CO2-free hydrogen and hydrogen-rich syngas, eliminating the conundrum of carbon utilization. Firstly, the various types of carbon that are known to result during the pyrolysis process and their dependencies on the reaction conditions for catalytic and noncatalytic systems are summarized. The synchronization of the reactions’ kinetics is considered to be of paramount importance for efficient performance. This translates to the necessity of finding suitable reaction conditions, carbon reactivities, and catalysts that might enable control over competing reactions through the manipulation of the reaction rates. As a consequence, the reaction kinetics of methane pyrolysis is then emphasized, followed by the particularities of carbon deposition and the kinetics of carbon gasification. Given the urgency in finding suitable solutions for decarbonizing the energy sector and the limited information on the gasification of pyrolytic carbon, more research is needed and encouraged in this area. In order to provide CO2-free hydrogen production, the reaction heat should also be provided without CO2. Electrification is one of the solutions, provided that low-carbon sources are used to generate the electricity. Power-to-heat, i.e., where electricity is used for heating, represents the first step for the chemical industry.

Abstract: Sodium-ion batteries are attracting great attention due to their low cost and abundance of sodium. The O3-type NaNi1/3Fe1/3Mn1/3O2 layered oxide material is a promising candidate for positive electrodes (cathodes) in Na-ion batteries. However, its stable electrochemical performance is restricted by the upper voltage limit of 4.0 V (vs Na/Na+), which allows for reversibly removing 0.5-0.55 Na+ per formula unit, corresponding to the capacity of 120-130 mAh.g(-1). Further reduction of sodium content inevitably accelerates capacity degradation, and this issue calls for a detailed study of the redox reactions that accompany the electrochemical (de)intercalation of a large amount of sodium. Here, we present operando and ex situ studies using powder X-ray diffraction and X-ray absorption spectroscopy combined with Fe-57 Mossbauer spectroscopy. Our approach reveals the sequence of the redox transitions that occur during the charge and discharge of O3-NaNi1/3Fe1/3Mn1/3O2. Our data show that in addition to nickel and iron cations oxidizing to M+4, a part of iron transforms into the “3 + delta” state owing to the fast electron exchange Fe3+ + Fe4+ <-> Fe4+ + Fe3+. This process freezes upon cooling the material to 35 K, producing Fe4+ cations, some of which occupy tetrahedral positions.

Abstract: Our scientific and technological worldviews are largely dominated by the concepts of entropy and complexity. Originating in 19th-century thermodynamics, the concept of entropy merged with information in the last century, leading to definitions of entropy and complexity by Kolmogorov, Shannon and others. In its simplest form, this worldview is an application of the normal rules of arithmetic. In this worldview, when tossing a coin, a million heads or tails in a row is theoretically possible, but impossible in practice and in real life. On this basis, the impossible (in the binary case, the outermost entries of Pascal's triangle xn and yn for large values of n) can be safely neglected, and one can concentrate fully on what is common and what conforms to the law of large numbers, in fields ranging from physics to sociology and everything in between. However, in recent decades it has been shown that what is most improbable tends to be the rule in nature. Indeed, if one combines the outermost entries xn and yn with the normal rules of arithmetic, either addition or multiplication, one obtains Lamé curves and power laws respectively. In this article, some of these correspondences are highlighted, leading to a double conclusion. First, Gabriel Lamé's geometric footprint in mathematics and the sciences is enormous. Second, conic sections are at the core once more. Whereas mathematics so far has been exclusively the language of patterns in the sciences, the door is opened for mathematics to also become the language of the individual. The probabilistic worldview and Lamé's footprint can be seen as dual methods. In this context, it is to be expected that the notions of information, complexity, simplicity and redundancy benefit from this different viewpoint.

Abstract: Microalgae can play a key role in the bioeconomy, particularly in combination with the valorisation of waste streams as cultivation media. Urine is an example of a widely available nutrient-rich waste stream, and alkaline stabilization and subsequent full nitrification in a bioreactor yields a stable nitrate-rich solution. In this study, such nitrified urine served as a culture medium for the edible microalga Limnospira indica. In batch cultivation, nitrified urine without additional supplements yielded a lower biomass concentration, nutrient uptake and protein content compared to modified Zarrouk medium, as standard medium. To enhance the nitrogen uptake efficiency and biomass production, nitrified urine was supplemented with potentially limiting elements. Limited amounts of phosphorus (36 mg L−1), magnesium (7.9 mg L−1), calcium (12.2 mg L−1), iron (2.0 mg L−1) and EDTA (88.5 mg Na2-EDTA.2H2O L−1) rendered the nitrified urine matrix as effective as modified Zarrouk medium in terms of biomass production (OD750 of 1.2), nutrient uptake (130 mg N L−1) and protein yield (47%) in batch culture. Urine precipitates formed by alkalinisation could in principle supply enough phosphorus, calcium and magnesium, requiring only external addition of iron, EDTA and inorganic carbon. Subsequently, the suitability of supplemented nitrified urine as a culture medium was confirmed in continuous Limnospira cultivation in a CSTR photobioreactor. This qualifies nitrified urine as a valuable and sustainable microalgae growth medium, thereby creating novel nutrient loops on Earth and in Space, i.e., in regenerative life support systems for human deep-space missions.

Abstract: In this paper convexity constraints are derived for a background model of electron energy loss spectra (EELS) that is linear in the fitting parameters. The model outperforms a power-law both on experimental and simulated backgrounds, especially for wide energy ranges, and thus improves elemental quantification results. Owing to the model’s linearity, the constraints can be imposed through fitting by quadratic programming. This has important advantages over conventional nonlinear power-law fitting such as high speed and a guaranteed unique solution without need for initial parameters. As such, the need for user input is significantly reduced, which is essential for unsupervised treatment of large datasets. This is demonstrated on a demanding spectrum image of a semiconductor device sample with a high number of elements over a wide energy range.

Abstract: Correction for ‘From the Birkeland–Eyde process towards energy-efficient plasma-based NO_{<italic>X</italic>}synthesis: a techno-economic analysis’ by Kevin H. R. Rouwenhorst<italic>et al.</italic>,<italic>Energy Environ. Sci.</italic>, 2021,<bold>14</bold>, 2520–2534, https://doi.org/10.1039/D0EE03763J.

Abstract: Carbon dioxide electrochemical reduction (CO2ER) has attracted considerable attention as a technology to recycle CO2 into raw materials for chemicals using renewable energies. We recently found that Zn-Al layered double hydroxides (Zn-Al LDH) have the CO-forming CO2ER activity. However, the activity was only evaluated by using the liquid-phase CO2ER. In this study, Ni-Al and Ni-Fe LDHs as well as Zn-Al LDH were synthesized using a facile coprecipitation process and the gas-phase CO2ER with the LDH-loaded gas-diffusion electrode (GDE) was examined. The products were characterized by XRD, STEM-EDX, BF-TEM and ATR-IR spectroscopy. In the ATR-IR results, the interaction of CO2 with Zn-Al LDH showed a different carbonates evolution with respect to other LDHs, suggesting a different electrocatalytic activity. The LDH-loaded GDE was prepared by simple drop-casting of a catalyst ink onto carbon paper. For gas-phase CO2ER, only Zn-Al LDH exhibited the CO2ER activity for carbon monoxide (CO) formation. By using different potassium salt electrolytes affording neutral to strongly basic conditions, such as KCl, KHCO3 and KOH, the gas-phase CO2ER with Zn-Al LDH-loaded GDE showed 1.3 to 2.1 times higher partial current density for CO formation than the liquid-phase CO2ER.

Abstract: New Cinema History broadened film studies by emphasising the complexity of cinema as a multifaceted phenomenon that includes the socio-economic context in which films were made, circulated, shown and received. As part of the digital turn, the discipline adopted computational methods and created quantitative research data to research this socio-economic context at scale. However, not all datasets created in this context adhere to FAIR principles, decreasing their reusability. By reconciling 14 cinema-related datasets, Cinema Belgica facilitates research into the history of Belgian cinema. This research paper documents and critically reflects on the choices made when selecting, modelling and reconciling information for the Cinema Belgica database.

Abstract: Cold atmospheric plasma (CAP) is a partially ionized gas that gains attention
as a well-tolerated cancer treatment that can enhance anti-tumor immune
responses, which are important for durable therapeutic effects. This review
offers a comprehensive and critical summary on the current understanding of
mechanisms in which CAP can assist anti-tumor immunity: induction of
immunogenic cell death, oxidative post-translational modifications of the
tumor and its microenvironment, epigenetic regulation of aberrant gene
expression, and enhancement of immune cell functions. This should provide
a rationale for the effective and meaningful clinical implementation of CAP. As
discussed here, despite its potential, CAP faces different clinical limitations
associated with the current CAP treatment modalities: direct exposure of
cancerous cells to plasma, and indirect treatment through injection of
plasma-treated liquids in the tumor. To this end, a novel modality is proposed:
plasma-treated hydrogels (PTHs) that can not only help overcome some of the
clinical limitations but also offer a convenient platform for combining CAP
with existing drugs to improve therapeutic responses and contribute to the
clinical translation of CAP. Finally, by integrating expertise in biomaterials and
plasma medicine, practical considerations and prospective for the
development of PTHs are offered.

Abstract: Mannosylerythritol lipids (MELs) are a promising group of biosurfactants due to their high fermentation yield, selfassembly and biological activity. During fermentation by Pseudozyma aphidis, a mixture of MELs with different levels of acylation is formed, of which the fully deacetylated form is the most valuable. In order to reduce the environmental impact of deacetylation, an enzymatic process using natural deep eutectic solvents (NADES) has been developed. We tested the deacetylation of a purified MELs mixture with immobilized Candida antarctica lipase B enzyme and 2-ethylhexanol as co-substrate in 140 h reactions with different NADES. We identified hydrophobic NADES systems with similar yields and kinetics as in pure 2-ethylhexanol solvent. Our results indicate that deacetylation of MELs mixtures in NADES as a solvent is possible with yields comparable to pure co-substrate and that hydrophobic NADES without carboxylic acid compounds facilitate the reaction to the greatest extent.