Inés Puente-Orench

Scrutinizing the role of size reduction on the exchange bias and dynamic magnetic behavior in NiO nanoparticles.

NiO nanoparticles (NPs) with a nominal size range of 2-10 nm, synthesized via high-temperature pyrolysis of a nickel nitrate, have been extensively investigated using neutron diffraction and magnetic (ac and dc) measurements. The magnetic behavior of the NPs changes noticeably when their diameter decreases below 4 nm. For NPs larger than or equal to this size, Rietveld analysis of the room temperature neutron diffraction patterns reveals that there is a reduction in the expected magnetic moment per [Formula: see text] ion with respect to bulk NiO, which is linked to the existence of a magnetically disordered shell at the NP surface. The presence of two peaks in the temperature dependence of both the dc magnetization after zero-field-cooling and the real part of the ac magnetic susceptibility is explained in terms of a core (antiferromagnetic, AFM)/shell (spin glass, SG) morphology. The high-temperature peak ([Formula: see text] K) is associated with collective blocking of the uncompensated magnetic moments inside the AFM core. The low-temperature peak ([Formula: see text] K) is a signature of a SG-like freezing of the surface [Formula: see text] spins. In addition, an exchange bias (EB) effect emerges due to the core/shell magnetic coupling. The cooling field and temperature dependences of the EB effect and the coercive field are discussed in terms of the core size and the effective magnetic anisotropy of the NPs. However, NiO NPs of 2 nm in size no longer show AFM order and the [Formula: see text] magnetic moments freeze into a SG-like state below [Formula: see text] K, with no evidence of EB effect.

Addressed realization of multication complex arrangements in metal-organic frameworks

A method to control the arrangement of various metal elements in MOFs at atomic and mesoscopic scales is described. The preparation of materials with structures composed of multiple metal cations that occupy specific sites is challenging owing to the difficulty of simultaneously addressing the incorporation of different elements at desired precise positions. We report how it is possible to use a metal-organic framework (MOF) built with a rod-shaped inorganic secondary building unit (SBU) to combine multiple metal elements at specific positions in a manner that is controllable at atomic and mesoscopic scales. Through the combination of four different metal elements at judiciously selected molar ratios, 20 MOFs of different compositions and the same topology have been prepared and characterized. The use of diffraction techniques, supported by density functional theory calculations, has led us to determine various possible atomic arrangements of the metal cations within the SBUs. In addition, seven of the compounds combine multiple types of atomic arrangements, which are mesoscopically distributed along the crystals. Given the large diversity and importance of rod-based MOFs, we believe that these findings offer a new general strategy to produce complex materials with required compositions and controllable arrangements of the metal cations for desired applications.

Size effects on the Néel temperature of antiferromagnetic NiO nanoparticles

Among all antiferromagnetic transition metal monoxides, NiO presents the highest Neel temperature (TN ∼ 525 K). In this work, the size-dependent reduction of TN in NiO nanoparticles with average diameters (D) ranging from 4 to 9 nm is investigated by neutron diffraction. The scaling law followed by TN(D) is in agreement with the Binder theory of critical phenomena in low-dimensional systems. X-ray absorption fine structure measurements link the decrease of TN to the occurrence of size effects (average undercoordination, bond relaxation and static disorder) in the nearest and next-nearest Ni coordination shells that hold the key for the maintenance of the antiferromagnetic order.

Neutron Diffraction Studies of the Molecular Compound [Co2(bta)]n (H4bta =1,2,4,5-Benzenetetracarboxylic Acid): In the Quest of Canted Ferromagnetism

The exchange mechanism and magnetic structure of the organic-inorganic layered molecule-based magnet [Co2(bta)]n (1) (H4bta =1,2,4,5-benzenetetracarboxylic acid) have been investigated through variable-temperature magnetic susceptibility measurements and supported with a series of neutron diffraction experiments. Cryomagnetic studies have shown an antiferromagnetic ordering at a transition temperature of 16 K that is followed by the appearance of a weak ferromagnetism below 11 K. The weak antiferromagnetic interlayer interaction plays an important role in this system in spite of the long interlayer separation. A ferromagnetic ordering is induced by applied magnetic fields greater than 1800 G (metamagnetic behavior), and a slow magnetic relaxation from this ferromagnetic phase to the antiferromagnetic one is observed. The magnetic structure of 1 has been elucidated at low temperatures in zero field by neutron powder diffraction measurements and was found to be of antiferromagnetic nature with the local cobalt(II) spins (magnetic moments) being aligned ferromagnetically in the ac plane and antiferromagnetically coupled along the crystallographic b axis. No evidence for a long-range spontaneous ferromagnetic component below 11 K was observed in the neutron experiment.

Localized translational motions in semicrystalline poly(ethylene terephthalate) studied by incoherent quasielastic neutron scattering

Abstract.One of the simplest ways to confine polymeric materials is by self-assembling during the crystallization process. The remaining amorphous phase is then constrained by the lamellar crystals. In this manuscript, we aim to shed additional light in the understanding of the amorphous chains dynamics of semicrystalline polymers above the Tg by using incoherent quasielastic neutron scattering QENS in a nanoscopic time scale (10-9-10-10s) on poly(ethylene terephthalate). The observed dynamics is satisfactorily described by a theoretical model that considers that the proton mobility follows a random jump-diffusion in a restricted environment. We demonstrate that the combination of macroscopic with nanoscopic dynamic tools allows a complete description of the confined dynamics on a paradigmatic semicrystalline polymer like poly(ethylene terephthalate).Graphical abstract

Neutron diffraction and magnetism of CoO antiferromagnetic nanoparticles

We report a study on neutron diffraction and magnetic properties ol cobalt oxide CoO antiferromagnetic nanoparticles with different sizes. The nanoparticles are composed by a structurally and magnetically ordered core and a structurally ordered and magnetically disordered shell with a thickness of about 2 nm. The ordered core has cell parameters, moments direction and modulus similar to those of bulk CoO. Small differences found are attributed to an increase of the oxidation of the nanoparticles with the decrease of size. A remanent moment Mr can be induced in CoO nanoparticles by crossing the transition temperature in the presence of a magnetic field, while the magnetic structure of the antiferromagnetically ordered moments of the nanoparticles core remains unchanged after field cooling within the experimental precision, suggesting that Mr arises in the magnetically disordered shell.

Disclosure of Double Exchange Bias Effect in Chromium (III) Oxide Nanoparticles

In the last decade, the renewed interest in antiferromagnetic (AF) magnetoelectric (ME) materials has been driven by the challenging multifunctionality of spintronic devices. One of the most ambitious goals is to build exchange-biased ferromagnetic/AF junctions with electric field-controlled properties. In this context, the understanding of the modifications that size reduction induces in the magnetic properties of a material being both AF and ME holds the key to control the magnetic coupling at the interface. Here, we show that the spin arrangement in chromium (III) oxide core/shell nanoparticles changes significantly as a function of the radial distance from the nanoparticle center. While the nanoparticle core retains an AF structure, magnetic moments located on a thin surface shell are in a disordered spin-glass (SG)-like state. In addition, canted spins develop at the boundary of the ME AF core. These spins, which mediate a moderate AF/SG exchange coupling at low temperature, are exchange coupled to the AF core, thus giving rise to a lower yet more robust exchange bias effect, which persists up to the Néel temperature of the AF core.

On the exchange bias effect in NiO nanoparticles with a core(antiferromagnetic)/shell (spin glass) morphology

The unexpected appearance of magnetic hysteresis and exchange bias effects in nominally antiferromagnetic NiO nanoparticles is usually explained in terms of a core/shell morphology, where a spin glass-like shell is exchange coupled to an antiferromagnetic core. However, recent studies have challenged the validity of this assumption for small enough NiO nanoparticles. In this work we present proof of the core/shell model for NiO nanoparticles with sizes below 10 nm by combining neutron powder diffraction and magnetic measurements. In addition, we have verified that the exchange bias effect persists even when the particle size is reduced down to 4 nm.

Changes in mobility of plastic crystal ethanol during its transformation into the monoclinic crystal state

Transformation of deuterated ethanol from the plastic crystal phase into the monoclinic one is investigated by means of a singular setup combining simultaneously dielectric spectroscopy with neutron diffraction. We postulate that a dynamic transition from plastic crystal to supercooled liquid-like configuration through a deep reorganization of the hydrogen-bonding network must take place as a previous step of the crystallization process. Once these precursor regions are formed, subsequent crystalline nucleation and growth develop with time.

Oxygen Evolution Reaction on Perovskites: A Multieffect Descriptor Study Combining Experimental and Theoretical Methods

The correlation between ex situ electronic conductivity, oxygen vacancy content, flat-band potential (Efb), and the oxygen evolution reaction (OER) activity for a wide range of perovskite compositions [La1–xSrxCoO3−δ series (with x = 0, 0.2, 0.4, 0.6, 0.8), LaMO3−δ series (M = Cr, Mn, Fe, Co, Ni), Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF), and PrBaCo2O6−δ (PBCO)] are investigated experimentally and theoretically. It is found that all of these parameters can affect the OER activity; however, none of them alone play a crucial role in determining the electrocatalytic activity. The correlation of one single physicochemical property with the OER activity always presents deviation points, indicating that a limitation does exist for such 2-dimensional correlations. Nevertheless, these deviations can be explained considering other physicochemical properties and their correlation with the OER activity. Hence, this work aims in simultaneously linking the OER activity with several physicochemical materials properties. The con...