Electronic and Structural Disorder of the Epitaxial La_0.67Sr_0.33MnO₃ Surface

Understanding and tuning epitaxial complex oxide films are crucial in controlling the behavior of devices and catalytic processes. Substrate-induced strain, doping, and layer growth are known to influence the electronic and magnetic properties of the bulk of the film. In this study, we demonstrate a clear distinction between the bulk and surface of thin films of La0.67Sr0.33MnO3 in terms of chemical composition, electronic disorder, and surface morphology. We use a combined experimental approach of X-ray-based characterization methods and scanning probe microscopy. Using X-ray diffraction and resonant X-ray reflectivity, we uncover surface nonstoichiometry in the strontium and lanthanum alongside an accumulation of oxygen vacancies. With scanning tunneling microscopy, we observed an electronic phase separation (EPS) on the surface related to this nonstoichiometry. The EPS is likely driving the temperature-dependent resistivity transition and is a cause of proposed mixed-phase ferromagnetic and paramagnetic states near room temperature in these thin films.</p

Orbital-overlap-driven hybridization in 3d-transition metal perovskite oxides LaMO₃ (M = Ti-Ni) and La₂CuO₄

The wide tunability of strongly correlated transition metal (TM) oxides stems from their complex electronic properties and the coupled degrees of freedom. Among the perovskite oxides family, LaMO3 (M = Ti-Ni) allows an M-dependent systematic study of the electronic structure within the same-structure-family motif. While most of the studies have been focusing on the 3d TMs and oxygen sites, the role of the rare-earth site has been far less explored. In this work, we use resonant inelastic X-ray scattering (RIXS) at the lanthanum N4,5 edges and density functional theory (DFT) to investigate the hybridization mechanisms in LaMO3. We link the spatial-overlap-driven hybridization to energetic-overlap-driven hybridization by comparing the RIXS chemical shifts and the DFT band widths. The scope is extended to highly covalent Ruddlesden-Popper perovskite La2CuO4 by intercalating lanthanum atoms to rock-salt layers. Our work evidences an observable contribution of localized lanthanum 5p and 4f orbitals in the band structure.</p

Deeper mechanistic insights into epitaxial nickelate electrocatalysts for the oxygen evolution reaction

Mass production of green hydrogen via water electrolysis requires advancements in the performance of electrocatalysts, especially for the oxygen evolution reaction. In this feature article, we highlight how epitaxial nickelates act as model systems to identify atomic-level composition-structure-property-activity relationships, capture dynamic changes under operating conditions, and reveal reaction and failure mechanisms. These insights guide advanced electrocatalyst design with tailored functionality and superior performance. We conclude with an outlook for future developments via operando characterization and multilayer electrocatalyst design

Balancing Partial Ionic and Electronic Transport for Optimized Cathode Utilization of High-Voltage LiMn2O4/Li3InCl6 Solid-State Batteries

Their suggested stability towards high-voltage cathode materials makes halide-based solid electrolytes currently an interesting class of ionic conductors for solid-state batteries. Especially the LiMn2O4 spinel cathode active material is of interest due to its slightly higher nominal voltage and more resilience to overcharging compared to LiCoO2 and LiNixMnyCozO2 cathodes. Typically, a standard ratio of active material to solid electrolyte is used in composites for solid-state batteries. However, for ideal transport properties, and thus to achieve balanced and optimal partial-conductivities, this ratio needs to be re-optimized each time the material basis is changed. In this work, we show transport in the composite measured through both DC polarization as well as transmission line modeling of the impedance spectra. By balancing the partial transport parameters of the composite, an optimum capacity of the solid-state batteries is achieved. This work shows characterization and optimization of transport is required for unlocking the full potential of solid-state batteries

Vapor Swelling of Polymer Brushes Compared to Nongrafted Films

Polymer brushes, coatings of polymers covalently end-grafted to a surface, have been proposed as a more stable alternative to traditional physisorbed coatings. However, when such coatings are applied in settings such as vapor sensing and gas separation technologies, their responsiveness to solvent vapors becomes an important consideration. It can be anticipated that the end-anchoring in polymer brushes reduces the translational entropy of the polymers and instead introduces an entropic penalty against stretching when vapor is absorbed. Therefore, swelling can be expected to be diminished in brushes compared to nongrafted films. Here, we study the effect of the anchoring-constraint on vapor sorption in polymer coatings using coarse-grained molecular dynamics simulations as well as humidity-controlled ellipsometry on chemically identical polymer brushes and nongrafted films. We find a qualitative agreement between simulations and experiments, with both indicating that brushes certainly swell less than physisorbed films, although this effect is minor for common grafting densities. Our results imply that polymer brushes indeed hold great potential for the intended applications

Transcriptional metabolic inflexibility in skeletal muscle among individuals with increasing insulin resistance.

Disturbances in skeletal muscle lipid metabolism may play an important role in development of insulin resistance (IR). The aim was to investigate transcriptional control of skeletal muscle fatty acid (FA) metabolism in individuals with the metabolic syndrome (MetS) with varying degrees of insulin sensitivity (S(I)). 122 individuals with MetS (NCEP-ATP III criteria) at age 35-70 years, BMI 27-38 kg/m(2) were studied (subgroup EU-LIPGENE study). Individuals were divided into quartiles of S(I) measured during a frequently sampled insulin modified intravenous glucose tolerance test. Skeletal muscle normalized mRNA expression levels of genes important in skeletal muscle FA handling were analyzed with quantitative real-time PCR. The expression of sterol regulatory element binding protein 1c (SREBP1c), acetyl-CoA carboxylase 2 (ACC2), diacylglycerol acyltransferase (DGAT1), and nuclear respiration factor (NRF) was higher in the lowest two quartiles of S(I) (50th). Interestingly, peroxisome proliferator-activated receptor coactivator 1alpha (PGC1alpha), peroxisome proliferator-activated receptor alpha (PPARalpha), and muscle carnitine palmitoyl transferase 1b (mCPT1), important for oxidative metabolism, showed a complex mRNA expression profile; levels were lower in both the most "insulin sensitive" (IS) as well as the most "IR" individuals. Lipoprotein lipase (LPL) mRNA was reduced in the lowest quartile of S(I). Enhanced gene expression of SREBP1c and ACC2 in the IR state suggests a tendency towards FA storage rather than oxidation. From the lower expression of PGC1alpha, PPARalpha, and mCPT1 in both the most "IS" as well as the most "IR" individuals, it may be speculated that "IS" subjects do not need to upregulate these genes to have a normal FA oxidation, whereas the most "IR" individuals are inflexible in upregulating these genes