Spin-state Transition Research Articles

Spin-State Regulation of Perovskite Cobaltite to Realize Enhanced Oxygen Evolution Activity

Summary Perovskite electrocatalysts strongly rely on electronic structure regulation, especially for electron configuration (e g ) and conductivity. However, current regulation strategies inevitably involve ambiguous entanglement of crystals, electrons, and spin degrees of freedom. Here, we developed a spin-state regulation method to optimize oxygen evolution reaction (OER) activity by lattice orientation control of LaCoO 3 epitaxial films. The different lattice-oriented LaCoO 3 films bring different degrees of distortion of the CoO 6 octahedron, successfully inducing a spin-state transition of cobalt from a low spin state (LS t 2g 6 e g 0 ) to an intermediate spin state (IS t 2g 5 e g 1 ). X-ray absorption spectroscopy of Co L-edge and O K-edge provides experimental support of spin-state transition in different lattice-oriented LaCoO 3 films. As expected, LaCoO 3 (100) film possesses optimal e g electron filling, lower adsorption free energy, and higher conductivity, exhibiting better OER performance than the other two films. Our findings demonstrate that electronic state regulation will be a new avenue for the rational design of high-activity perovskite electrocatalysts.

Spectral Change in 3d–4f Resonant Inelastic X-ray Scattering of Ce Intermetallics Across the Transition between Kondo Singlet and Localized-Spin State

The spectral change in the 3d resonant X-ray inelastic scattering (RIXS) induced by the spin-state transition between Kondo singlet (KS) and localized spin (LS) state is theoretically investigated for γ-like Ce intermetallics by means of a single impurity Anderson model. The basis configurations with an electron–hole pair are included in the calculation within the configuration interaction scheme, in addition to the intra-atomic full multiplet coupling of the Ce impurity. A distinct spectral change is found across the KS–LS transition in the RIXS excited at the charge-transfer satellite of the 3d X-ray absorption spectrum (XAS) under a polarized geometry. In contrast, the 3d XAS and RIXS spectra under a depolarized geometry are rather insensitive to the spin-state transition.

A spin transition mechanism for cooperative adsorption in metal-organic frameworks.

Cooperative binding, whereby an initial binding event facilitates the uptake of additional substrate molecules, is common in biological systems such as haemoglobin. It was recently shown that porous solids that exhibit cooperative binding have substantial energetic benefits over traditional adsorbents, but few guidelines currently exist for the design of such materials. In principle, metal-organic frameworks that contain coordinatively unsaturated metal centres could act as both selective and cooperative adsorbents if guest binding at one site were to trigger an electronic transformation that subsequently altered the binding properties at neighbouring metal sites. Here we illustrate this concept through the selective adsorption of carbon monoxide (CO) in a series of metal-organic frameworks featuring coordinatively unsaturated iron(ii) sites. Functioning via a mechanism by which neighbouring iron(ii) sites undergo a spin-state transition above a threshold CO pressure, these materials exhibit large CO separation capacities with only small changes in temperature. The very low regeneration energies that result may enable more efficient Fischer-Tropsch conversions and extraction of CO from industrial waste feeds, which currently underutilize this versatile carbon synthon. The electronic basis for the cooperative adsorption demonstrated here could provide a general strategy for designing efficient and selective adsorbents suitable for various separations.

Perovskite-Type InCoO3 with Low-Spin Co3+: Effect of In-O Covalency on Structural Stabilization in Comparison with Rare-Earth Series.

Perovskite rare-earth cobaltites ACoO3 (A = Sc, Y, La-Lu) have been of enduring interest for decades due to their unusual structural and physical properties associated with the spin-state transitions of low-spin Co3+ ions. Herein, we have synthesized a non-rare-earth perovskite cobaltite, InCoO3, at 15 GPa and 1400 °C and investigated its crystal structure and magnetic ground state. Under the same high-pressure and high-temperature conditions, we also prepared a perovskite-type ScCoO3 with an improved cation stoichiometry in comparison to that in a previous study, where synthesis at 6 GPa and 1297 °C yielded a perovskite cobaltite with cation mixing on the A-site, (Sc0.95Co0.05)CoO3. The two perovskite phases have nearly stoichiometric cation compositions, crystallizing in the orthorhombic Pnma space group. In the present investigation, comprehensive studies on newly developed and well-known Pnma ACoO3 perovskites (A = In, Sc, Y, Pr-Lu) show that InCoO3 does not fulfill the general evolution of crystal metrics with A-site cation size, indicating that InCoO3 and rare-earth counterparts have different chemistry for stabilizing the Pnma structures. Detailed structural analyses combined with first-principles calculations reveal that the origin of the anomaly for InCoO3 is ascribed to the A-site cation displacements that accompany octahedral tilts; despite the highly tilted CoO6 network, the In-O covalency makes In3+ ions reluctant to move from their ideal cubic-symmetry position, leading to less orthorhombic distortion than would be expected from electrostatic/ionic size mismatch effects. Magnetic studies demonstrate that InCoO3 and ScCoO3 are diamagnetic with a low-spin state of Co3+ below 300 K, in contrast to the case of (Sc0.95Co0.05)CoO3, where the high-spin Co3+ ions on the A-site generate a large paramagnetic moment. The present work extends the accessible composition range of the low-spin orthocobaltite series and thus should help to establish a more comprehensive understanding of the structure-property relation.

Pressure-induced spin-state transition of iron in magnesiowüstite (Fe,Mg)O

We present a detailed theoretical study of the electronic, magnetic, and structural properties of magnesiow\"ustite Fe$_{1-x}$Mg$_x$O with $x$ in the range between 0$-$0.875 using a fully charge self-consistent implementation of the density functional theory plus dynamical mean-field theory (DFT+DMFT) method. In particular, we compute the electronic structure and phase stability of the rock-salt B1-structured (Fe,Mg)O at high pressures relevant for the Earth's lower mantle. We obtain that upon compression paramagnetic (Fe,Mg)O exhibits a spin-state transition of Fe$^{2+}$ ions from a high-spin to low-spin (HS-LS) state which is accompanied by a collapse of local magnetic moments. The HS-LS transition results in a substantial drop of the lattice volume by about 4$-$8 %, implying a complex interplay between electronic and lattice degrees of freedom. Our results reveal a strong sensitivity of the calculated transition pressure $P_{\rm tr.}$ upon addition of Mg. While for Fe-rich magnesiow\"ustite, Mg $x < 0.5$, $P_{\rm tr.}$ exhibits a rather weak variation at $\sim$80 GPa, for Fe-poor (Fe,Mg)O it drops, e.g., by about 35 % to 52 GPa for Mg $x=0.75$. This behavior is accompanied by a substantial change of the spin transition range from 50$-$140 GPa in FeO to 30$-$90 GPa for $x=0.75$. In addition, the calculated bulk modulus (in the HS state) is found to increase by $\sim$12 % from 142 GPa in FeO to 159 GPa in (Fe,Mg)O with Mg $x=0.875$. We find that the pressure-induced HS-LS transition has different consequences for the electronic properties of the Fe-rich and poor (Fe,Mg)O. For the Fe-rich (Fe,Mg)O, the transition is found to be accompanied by a Mott insulator to (semi-) metal phase transition. In contrast to that, for $x>0.25$, (Fe,Mg)O remains insulating up to the highest studied pressures, implying a Mott insulator to band insulator phase transition at the HS-LS transformation.

Thermally Induced Spin State Transition in LiCoO2 and Its Effects on Battery Performance

LiCoO2 is the most widely used and extensively studied cathode material for Li-ion batteries. The studies based on the improvement of the performance have focused on the structural and electrochemical properties of LiCoO2. However, significantly less attention has been paid to its magnetic properties and their effects on battery performance. For the first time to our knowledge, we report a thermally induced magnetic spin state transition from low spin (LS) to intermediate spin (IS) at ∼800K in bulk LiCoO2 via magnetic susceptibility measurements. We quench the LiCoO2 from above the spin state transition temperature (∼810K) into liquid nitrogen to preserve the IS state at room temperature. We use this quenched sample (q-LiCoO2) as an active cathode material. We observe a significant improvement (∼15% better capacity retention after 200 cycles at 1C) in cell performance of q-LiCoO2 compared to the ref-LiCoO2 which is used as a reference material. Our results show that it is possible to tailor the magnetic properties and electronic structure of cathode materials to achieve better battery performance.

Synthesis, Crystal Structures and Magnetic Properties of Composites Incorporating an Fe(II) Spin Crossover Complex and Polyoxometalates

[Fe(dppOH)2]2+ (dppOH = 2,6-di(pyrazol-1-yl)-4-(hydroxymethyl)pyridine) is known to show spin crossover (SCO) behavior and light-induced excited spin state transitions (LIESST). Here, we show that the SCO properties of the [Fe(dppOH)2]2+ complex can be altered by a crystal engineering approach employing counter anion exchange with polyoxometalate (POM) anions. Using this strategy, two new composite materials (TBA)[Fe(dppOH)2][PMo12O40] (1) and [Fe(dppOH)2]3[PMo12O40]2 (2) (TBA = tetra-n-butylammonium) have been isolated and studied by single crystal X-ray diffraction and magnetic susceptibility measurements. 1 was found to be in a high spin state at 300 K and showed no spin crossover behavior due to a dense packing structure induced by hydrogen bonding between the hydroxyl group of the dppOH ligands and the POM anions. Conversely, 2 contains two crystallographically unique Fe centers, where one is in the low spin state whilst the other is locked in a high spin state in a manner analogous to 1. As a result, 2 was found to show partial spin crossover behavior around 230 K with a decrease in the χmT value of 1.9 emu·mol−1·K. This simple approach could therefore provide a useful method to aid in the design of next generation spin crossover materials.

Colossal thermopower, spin states and delocalization effects in single layered La2−xSrxCoO4

Hole-doped La2CoO4 compounds have been widely studied due to their multifaceted behavior such as charge ordering, spin ordering and spin blockade. Hole doping in La2CoO4 causes appearance of the Co3+ along with the Co2+, which makes it an interesting model system for study of the spin-state transitions. In hole-doped samples, the spin-states of the Co3+ ions at large have been reported as the low or intermediate state. We report here a study on the Sr doping in La2CoO4. The Sr doping has been found to stabilize the crystal structure. By combining structural, electronic structure and electrical transport results, it is observed that the high-spin state is present in all the La2−xSrxCoO4 (x = 0.5, 0.8, 0.9 and 1.0) samples. The high-spin state has been found to be concomitant with the delocalization of the eg electrons. In addition, in these materials, a colossal thermopower has been observed for first time in the cryogenic temperatures.

Relation between the Co-O bond lengths and the spin state of Co in layered Cobaltates: a high-pressure study

The pressure-response of the Co-O bond lengths and the spin state of Co ions in a hybrid 3d-5d solid-state oxide Sr2Co0.5Ir0.5O4 with a layered K2NiF4-type structure was studied by using hard X-ray absorption and emission spectroscopies. The Co-K and the Ir-L3 X-ray absorption spectra demonstrate that the Ir5+ and the Co3+ valence states at ambient conditions are not affected by pressure. The Co Kβ emission spectra, on the other hand, revealed a gradual spin state transition of Co3+ ions from a high-spin (S = 2) state at ambient pressure to a complete low-spin state (S = 0) at 40 GPa without crossing the intermediate spin state (S = 1). This can be well understood from our calculated phase diagram in which we consider the energies of the low spin, intermediate spin and high spin states of Co3+ ions as a function of the anisotropic distortion of the octahedral local coordination in the layered oxide. We infer that a short in-plane Co-O bond length (<1.90 Å) as well as a very large ratio of Co-Oapex/Co-Oin-plane is needed to stabilize the IS Co3+, a situation which is rarely met in reality.

Valence and spin-state transition in cobaltates revisited by x-ray magnetic circular dichroism

Valence and spin-state transition in cobaltates revisited by x-ray magnetic circular dichroism

Magnetic evolution of nickel ion doped In2O3 nanocrystals under high magnetic field

High magnetic field (HMF) treatment is an important strategy to tune the physicochemical properties of traditional materials. Here, we take nickel ion doped In2O3 nanocrystals as an example and report that the magnetization behavior of diluted magnetic semiconductors can be easily tuned by HMF treatment. It is experimentally demonstrated that the room temperature ferromagnetism of lowly-doped nanocrystals can be greatly enhanced by HMF treatment while the paramagnetic properties of highly-doped samples is almost un-changed. These magnetic transition behaviors after HMF treatment are attributed to the rearrangement of magnetic ordering and the increment of grain-boundary defects. Our research not only points out an effective approach to induce the transition of spin states of diluted magnetic semiconductors but also provides a potentially efficient route to endow other traditional materials with novel physical properties.

Suppression of magnetism under pressure in FeS: A DFT+DMFT study

We show that evolution of magnetic properties in FeS under pressure cannot be explained only in terms of a spin state transition. While uniform compression does show substantial suppression of the local magnetic moment and increase of the weights of configurations with low spin, analysis of the local spin-spin correlation function demonstrates increase of the spin itinerancy. This is related to a strong modification of the electronic structure under pressure: in the high-pressure phase FeS is in the Fermi-liquid state, while decrease of the pressure moves the system to an orbital-selective regime.

Magnetic oxide thin solid films deposited at room temperature under ambient pressure using an electro-spray method

The deposition and characterization of magnetic metal-oxide, Eu1−xSrxCoO3 (x=0.2, 0.5) thin films using an electrostatic spray method are presented. The nano-sized particles were electro-sprayed from a colloidal suspension onto Pt/TiO2/SiO2/Si substrates at room temperature under ambient pressure. X-ray diffraction patterns showed a perovskite tetragonal structure with an I4/mmm space group. Optical and scanning electron microscopy of the thin films revealed their crack-free and uniform nature. The temperature-dependent magnetization showed a ferromagnetic-paramagnetic transition above 350K. Magnetic moments hysteresis loops demonstrate that the thin films exhibited a hard ferromagnetic state at 10K and a soft ferromagnetic one at room temperature. The Hall measurement revealed metallic behavior at room temperature, confirming the transition from a metallic state to an insulating one at T>300K. The correlation is explained based on the double exchange interaction and spin state transitions at both low and high temperatures.

Density functional study of the magneto-structural correlations of manganese complexes, [Mn2O2Hn(salpn)2]+(2−n) (n = 0–2) from the viewpoint of the protonation modes of the bridging oxygen anions

The magneto-structural correlations of [Mn2O2Hn(salpn)2]+(2−n) (n=0–2), for which the magnetic data were experimentally reported to strongly depend on the protonation modes, was investigated. First, the fully optimized geometries and the magnetic interactions of [Mn2O2Hn(salpn)2]+(2−n) (n=0–2) with using the B3LYP/LACVP∗ method was investigated, confirming that the dependencies of the Mn–Mn distances and of magnetic interactions on the protonation mode, n (n=0–2), are consistent with those experimentally reported. Further, describing the energy landscapes of both low-spin and high-spin states of these complexes for [Mn2O2] planes, it was found that the landscapes, in particular the positions of the lines where the stable spin-state transitions occur, depend on the protonation modes of the bridging oxygen anions. Further, the details of electronic structures behind the computational results on the basis of the natural orbital analyses were discussed.

Electrical resistivity anomaly, valence shift of Pr ion, and magnetic behavior in epitaxial (Pr1-yYy)1-xCaxCoO3 thin films under compressive strain

We have fabricated (Pr1−yYy)1-xCaxCoO3 (PYCCO) epitaxial films with various thicknesses by pulsed laser deposition on the SrLaAlO4 (SLAO) substrate that applied an in-plane compressive stress to the film, and investigated the temperature dependence of the electrical resistivity, ρ(T), of the films. An anomalous ρ(T) upturn with a broad hysteresis could be clearly observed only for the thinnest film (d = 50 nm), and the ρ(T) anomaly decreased by increasing film thickness, d. The temperature dependence of the X-ray absorption near-edge structure (XANES) spectra at Pr L2-edge was measured for the films, and the valence states of praseodymium (Pr) ion were determined using the analysis of the XANES spectra. As a result, the average valence of the Pr ion in the d = 50 nm film slightly increases with decreasing temperature from the common value of 3.0+ around room temperature to 3.15+ at 8 K. The valence shift of Pr is thus similar to what was observed on the PYCCO polycrystalline bulks with an abrupt metal-insulator transition, accompanied by a spin-state (SS) transition of Co ions. Furthermore, the low-temperature SQUID measurements evidenced a paramagnetic behavior down to the lowest temperature, which suggests that the dominant part of Co3+ ions in the film grown on the SLAO substrate tends to be in the low spin state characteristic for the insulating ground state. These results strongly suggest that the anomalous ρ(T) upturn in the thin films on the SrLaAlO4 (SLAO) substrate is closely related to the SS transition of Co ions. On the other hand, PYCCO films grown on the LaAlO3 (LAO) substrate that applied an in-plane tensile stress showed no valence shift of Pr ions and developed a long range ferromagnetic order, which points to a complete suppression of the low-temperature transition. The behaviors of the epitaxial films are discussed in terms of the in-plane stress exerted by different substrates and accumulated elastic energy.

A combined diffraction and EXAFS study of LaCoO3 and La0.5Sr0.5Co0.75Nb0.25O3 powders

A combination of neutron diffraction, synchrotron X-ray diffraction, and high-resolution extended X-ray absorption fine structure measurements has been used to clarify the correlations between long- and local-range structural distortions across the spin-state transition in powders of LaCoO3 and La0.5Sr0.5Co0.75Nb0.25O3. The analysis of the diffraction data has revealed that the isotropic thermal parameters of Co–O bond abnormally increase below 100 K in both samples, while the temperature dependence of the average Co–O bond lengths is linear from 10 to 300 K. We also have found that the Co–O bond lengths are larger in La0.5Sr0.5Co0.75Nb0.25O3, as compared with the ones in LaCoO3. The X-ray absorption data showed an anomalous decrease of the Co–O bond lengths only for LaCoO3, in contrast to the bond length values obtained by diffraction. The structural anomalies observed by spectroscopy measurements are discussed in terms of the spin-state transition model.

Anomalous behavior of displacement correlation function and strain in lanthanum cobalt oxide analyzed both from X-ray powder diffraction and EXAFS data

A combined X-ray powder diffraction (XPD) and high-resolution extended X-ray absorption fine structure (EXAFS) at the Co and Ga K-edges study has been performed for LaCoO3 and LaGaO3 ceramics, the latter sample was used as a reference without spin transitions. Based on the X-ray diffraction data, we have found that isotropic atomic displacement parameters (ADP) or mean-squared displacement of the Co–O bond exhibit gradual growth below ~50 K, wherein the strain dependencies testify rapid increase below 150 K for the LaCoO3 having rhombohedral structure. No similar features could be observed for LaGaO3 sample. Above ~100 K the isotropic ADP of the Co–O bond indicate a gradual growth, whereas strain curves show distinct bend near the spin-state transition temperature at about 150 K. According to the EXAFS data, the correlated parallel mean squared relative displacement (MSRD||) of Co–O and Ga–O bonds exhibit a gradual growth above 150 K; however, in the LaCoO3 this parameter is notably bigger. It is supposed that at low temperature the cobalt ions are dominantly in low-spin (LS) state, while certain amount of Co3+ ions located within the surface layer of the crystallines have high-spin state (HS). Temperature growth leads to a gradual transformation of the HS state of the cobalt ions into the highly-hybridized intermediate-spin (IS) state, while the cobalt ions located in the inner part of the crystallines remain LS configuration up to 150 K. Further temperature increase leads to a spin transition of the Co3+ ions located within the crystallines from the LS state into the IS one.

Investigation of Spin State Transition of [FeC17H31N7]2+ Compound by Using the Density Functional Method

The symmetry of the [FeC17H31N7]2+ novel compound is close to octahedral which has spin crossover properties (SCO). In this study, geometrical optimization, IR vibration frequencies, and HOMO-LUMO energy differences at various temperatures of the compound were calculated by DFT. It is realised that the computed splitting energies and splitting free enthalpies together with the mole fraction of HS state are compatible with the experiment.

Ligand Influence on Local Magnetic Moments in Fe-Based Metal–Organic Networks

Planar metal–organic networks are highly promising materials due to their modular nature and wide-ranging possible applications from spintronics up to biosensing. Spin state transitions connect local magnetic properties with structural modifications. In this paper, we report on ab initio calculations for two metal–organic planar networks, the Fe-phthalocyanine (Pc) polymer and its precursor material Fe-tetracyanobenzene (TCNB). The spin-polarized generalized gradient approximation to density functional theory with an explicit treatment of the Hubbard-U correction (SGGA+U) indicates a spin state transition between the well confirmed S = 1 state for Fe-Pc and a local, high-spin S = 2 state at the Fe site for Fe-TCNB. The high-spin state at the Fe site is confirmed by X-ray absorption spectroscopy (XAS) measurements of the Fe-TCNB network on the Au(111) substrate in connection with a multiplet analysis. We propose a possible spin state transition between Fe-TCNB and Fe-Pc by the on-surface synthesis of the l...

Optimization of thermoelectric properties in layered Bi2Sr2Co2Oy via high-magnetic-field sintering

Abstract Herein, we report the effect of the high-magnetic-field (HMF) sintering on the structural, electrical and thermal transport properties of the layered Bi2Sr2Co2Oy. Based on the results of x-ray diffraction and microtopography, we find the grains prefer to the oriented growth along the direction of applied magnetic field, leading to a higher textured degree and anisotropy. Correspondingly, the in-plane conductivity increases while the out-of-plane one reduces with increasing sintering magnetic field. At the same time, the in-plane thermopower shows an obvious enhancement after the HMF sintering, which mainly originates in the spin state transition of Co4+ ions. As a result, a remarkable enhancement of the in-plane thermoelectric figure-of-merit is obtained in the sample after the HMF sintering (8 T).