Cobalt-free layered perovskites RBaCuFeO5+δ (R = 4f lanthanide) as electrocatalysts for the oxygen evolution reaction.

Co-based perovskite oxides are intensively studied as promising catalysts for electrochemical water splitting in an alkaline environment. However, the increasing Co demand by the battery industry is pushing the search for Co-free alternatives. Here we report a systematic study of the Co-free layered perovskite family RBaCuFeO5+δ (R = 4f lanthanide), where we uncover the existence of clear correlations between electrochemical properties and several physicochemical descriptors. Using a combination of advanced neutron and X-ray synchrotron techniques with ab initio DFT calculations we demonstrate and rationalize the positive impact of a large R ionic radius in their oxygen evolution reaction (OER) activity. We also reveal that, in these materials, Fe3+ is the transition metal cation the most prone to donate electrons. We also show that similar R3+/Ba2+ ionic radii favor the incorporation and mobility of oxygen in the layered perovskite structure and increase the number of available O diffusion paths, which have an additional, positive impact on both, the electric conductivity and the OER process. An unexpected result is the observation of a clear surface reconstruction exclusively in oxygen-rich samples (δ > 0), a fact that could be related to their superior OER activity. The encouraging intrinsic OER values obtained for the most active electrocatalyst (LaBaCuFeO5.49), together with the possibility of industrially producing this material in nanocrystalline form should inspire the design of other Co-free oxide catalysts with optimal properties for electrochemical water splitting.

Charge Transfer and Orbital Reconstruction at an Organic-Oxide Interface.

The two-dimensional electron system (2DES) located at the surface of strontium titanate (STO) and at several other STO-based interfaces has been an established platform for the study of novel physical phenomena since its discovery. Here we report how the interfacing of STO and tetracyanoquinodimethane (TCNQ) results in a charge transfer that depletes the number of free carriers at the STO surface, with a strong impact on its electronic structure. Our study paves the way for efficient tuning of the electronic properties, which promises novel applications in the framework of oxide/organic-based electronics.

Amyloid-beta-copper interaction studied by simultaneous nitrogen K and copper L2,3 -edge soft X-ray absorption spectroscopy.

We study the interaction between amyloid ß (Aß) peptides and Cu and Zn metal ions by using soft X-ray absorption spectroscopy. The spectral features of the peptides and Cu are simultaneously characterized by recording spectra at the N K-edge and at the Cu L2,3 -edges. In the presence of the peptides, the Cu L2,3 -edge shows a fingerprint of monovalent Cu(I), caused by the interaction with the peptides. The appearance of Cu(I) is less significant at an acidic pH than at a basic pH. Furthermore, aggregation leads to a smaller signature of Cu(I). N K-edge spectra reveal that Cu and Zn ions exhibit a different coordination with the nitrogen atoms in the peptides. This suggests different roles of Cu and Zn in the peptide aggregation. Our work provides physical insight into the participation of the metal ions and Aß in the toxic reactive oxygen species formation.

Bad neighbour, good neighbour: how magnetic dipole interactions between soft and hard ferrimagnetic nanoparticles affect macroscopic magnetic properties in ferrofluids.

Fluids responding to magnetic fields (ferrofluids) offer a scene with no equivalent in nature to explore long-range magnetic dipole interactions. Here, we studied the very original class of binary ferrofluids, embedding soft and hard ferrimagnetic nanoparticles. We used a combination of X-ray magnetic spectroscopy measurements supported by multi-scale experimental techniques and Monte-Carlo simulations to unveil the origin of the emergent macroscopic magnetic properties of the binary mixture. We found that the association of soft and hard magnetic nanoparticles in the fluid has a considerable influence on their inherent magnetic properties. While the ferrofluid remains in a single phase, magnetic interactions at the nanoscale between both types of particles induce a modification of their respective coercive fields. By connecting the microscopic properties of binary ferrofluids containing small particles, our findings lay the groundwork for the manipulation of magnetic interactions between particles at the nanometer scale in magnetic liquids.

Direct Observation of Charge Transfer and Magnetism in Fe4Co4 Cyanide-Bridged Molecular Cubes.

We have studied the zero-dimensional cubane molecular correspondent of a Prussian blue analogue Cs-Fe4Co4 at low temperature and high magnetic field by means of L-edge X-ray absorption spectroscopy and X-ray magnetic circular dichroism. We probe the magnetic and electronic structures of Fe and Co separately upon light irradiation, which allows us to observe directly the electron transfer coupled to a spin transition phenomenon within the molecular cubes and to investigate the nature of the metastable photoexcited state. The magnetic moments in the photoexcited state are found to be M = 1.3µB ( Mspin = 0.59µB with large orbital moment, Morbit = 0.74µB) for low-spin FeIII and M = 1.5µB ( Mspin = 1.08µB with orbital moment, Morbit = 0.41µB) for high-spin CoII at 2 K and 6.8 T. From our results, we evidence that a strong antiferromagnetic coupling between the metal ions can be ruled out.

Non-empirical calculation of X-ray magnetic circular dichroism in lanthanide compounds.

Affordable calculations of X-ray magnetic circular dichroism and X-ray linear dichroism spectra of lanthanide ions purely based on structural input are difficult to achieve. Here we report on the successful application of ligand-field density-functional theory to obtain an exquisite reproduction of experimental spectra. As a testbed we use TbPc2 single-molecule magnets on a flat substrate.

Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes.

Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest--and more attractive--systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [Co(II)(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination--without nanoparticle aggregation and without complex dissociation--of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude.