Emergence of Metallic Conduction and Cobalt(II)-Based Single-Molecule Magnetism in the Same Temperature Range.

Single-molecule magnets exhibit magnetic bistabililties at the molecular level, making them promising for molecule-based spintronics due to high magnetic densities. The incorporation of SMM behavior and electrical conductivity in one compound is rare because these two physical properties often do not operate in the same temperature range, which further hinders their use in practical applications. Here we present an organic-inorganic molecular hybrid, ß″-(BEDO-TTF)3[Co(pdms)2]·(MeCN)(H2O)2 (BO3) (BEDO-TTF = bis(ethylenedioxy)tetrathiafulvalene and H2pdms = 1,2-bis(methanesulfonamido)benzene), which manifests both metallic conduction (electrical conductivity up to 1000 S cm-1 at 12 K under 2.0 gigapascal pressure) and SMM behavior in the temperature range 12-26 K for the first time.

Superionic Ag+ Conductor Ag17(CO3)3I11.

A new superionic Ag+ conductor with a nominal composition Ag17(CO3)3I11 (11AgI-3Ag2CO3) was found in the AgI-Ag2CO3 system. The conductor, which was formed at temperatures from 100 to 170 °C, is a metastable phase that gradually decomposes into AgI and Ag10(CO3)I4 over a period of a few weeks at room temperature (RT). A Ag+ ionic conductivity of 0.16 S/cm was measured at RT, and an activation energy of 0.33 eV was evaluated in the temperature range from -9 to 19 °C. Single-crystal X-ray analysis revealed that Ag17(CO3)3I11 crystallized in a rhombohedral unit cell with hexagonal parameters of a = 15.8831(6) Å and c = 30.0730(13) Å at -183 °C and space group R3c. The Ag atoms were distributed over 53 sites in the asymmetry unit, with a maximum occupancy of 0.33(8). The continuous distribution of the partially occupied Ag sites was associated with the conduction paths of the Ag+ ions in the structure.

Assessing nickel oxide electrocatalysts incorporating diamines and having improved oxygen evolution activity using operando UV/visible and X-ray absorption spectroscopy.

The electrolysis of water using renewable energy is a promising approach to developing a sustainable hydrogen-based economy. To improve the efficiency of this process, it will be necessary to develop highly active electrocatalysts that promote the oxygen evolution reaction (OER). In the present study, the OER activity of a nickel oxide electrocatalyst was dramatically improved following the addition of a diamine to the electrolyte solution during electrodeposition. Operando UV/vis absorption spectroscopy was used to assess a number of nickel catalysts containing various diamines and other organic compounds. The data indicate that Ni(II) complexes were formed with the diamines during electrodeposition. Consequently, the catalytic activity of these materials was enhanced based on increased concentrations of active reaction sites for the OER process. Ni K-edge X-ray absorption spectra showed that these catalysts were composed of γ-NiOOH with a Ni3.6+ valence state. The coordination of the diamine molecules to the γ-NiOOH produced structural distortion that contributed to improved OER activity. This structural distortion is likely the most important factor in enhancing the OER activity of inorganic-organic composite catalysts.

An Organic-Inorganic Hybrid Exhibiting Electrical Conduction and Single-Ion Magnetism.

The first three-dimensional (3D) conductive single-ion magnet (SIM), (TTF)2 [Co(pdms)2 ] (TTF=tetrathiafulvalene and H2 pdms=1,2-bis(methanesulfonamido)benzene), was electrochemically synthesised and investigated structurally, physically, and theoretically. The similar oxidation potentials of neutral TTF and the molecular precursor [HNEt3 ]2 [M(pdms)2 ] (M=Co, Zn) allow for multiple charge transfers (CTs) between the SIM donor [M(pdms)2 ]n- and the TTF.+ acceptor, as well as an intradonor CT from the pdms ligand to Co ion upon electrocrystallisation. Usually TTF functions as a donor, whereas in our system TTF is both a donor and an accepter because of the similar oxidation potentials. Furthermore, the [M(pdms)2 ]n- donor and TTF.+ acceptor are not segregated but strongly interact with each other, contrary to reported layered donor-acceptor electrical conductors. The strong intermolecular and intramolecular interactions, combined with CT, allow for relatively high electrical conductivity even down to very low temperatures. Furthermore, SIM behaviour with slow magnetic relaxation and opening of hysteresis loops was observed. (TTF)2 [Co(pdms)2 ] (2-Co) is an excellent building block for preparing new conductive SIMs.

Dynamic Behavior of Rh Species in Rh/Al2O3 Model Catalyst during Three-Way Catalytic Reaction: An Operando X-ray Absorption Spectroscopy Study.

The dynamic behavior of Rh species in 1 wt% Rh/Al2O3 catalyst during the three-way catalytic reaction was examined using a micro gas chromatograph, a NOx meter, a quadrupole mass spectrometer, and time-resolved quick X-ray absorption spectroscopy (XAS) measurements at a public beamline for XAS, BL01B1 at SPring-8, operando. The combined data suggest different surface rearrangement behavior, random reduction processes, and autocatalytic oxidation processes of Rh species when the gas is switched from a reductive to an oxidative atmosphere and vice versa. This study demonstrates an implementation of a powerful operando XAS system for heterogeneous catalytic reactions and its importance for understanding the dynamic behavior of active metal species of catalysts.

Slow Magnetic Relaxation in a Palladium-Gadolinium Complex Induced by Electron Density Donation from the Palladium Ion.

Incorporating palladium in the first coordination sphere of acetato-bridged lanthanoid complexes, [Pd2 Ln2 (H2 O)2 (AcO)10 ]⋅2 AcOH (Ln=Gd (1), Y (2), Gd0.4 Y1.6 (3), Eu (4)), led to significant bonding interactions between the palladium and the lanthanoid ions, which were demonstrated by experimental and theoretical methods. We found that electron density was donated from the d8 Pd2+ ion to Gd3+ ion in 1 and 3, leading to the observed slow magnetic relaxation by using local orbital locator (LOL) and X-ray absorption near-edge structure (XANES) analysis. Field-induced dual slow magnetic relaxation was observed for 1 up to 20 K. Complex 3 and frozen aqueous and acetonitrile solutions of 1 showed only one relaxation peak, which confirms the role of intermolecular dipolar interactions in slowing the magnetic relaxation of 1. The slow magnetic relaxation occurred through a combination of Orbach and Direct processes with the highest pre-exponential factor (τo =0.06 s) reported so far for a gadolinium complex exhibiting slow magnetic relaxation. The results revealed that transition metal-lanthanoid (TM-Ln) axial interactions indeed could lead to new physical properties by affecting both the electronic and magnetic states of the compounds.

Hofmeister Anion Effects on Protein Adsorption at an Air-Water Interface.

Hofmeister anion effects on adsorption kinetics of the positively charged lysozyme (pH < pI) at an air-water interface were studied by surface tension measurements and time-resolved X-ray reflectometry. In the salt-free solution, the protein adsorption rate increases with decreasing the net positive charge of lysozyme. When salt ions are dissolved in water, the protein adsorption rate drastically increases, and the rate is following an inverse Hoffmeister series (Br(-) > Cl(-) > F(-)). This is the result of the strongly polarized halide anion Br(-) being attracted to the adsorbed protein layer due to strong interaction with local electric field, while weakly polarized anion F(-) having no ability to penetrate the protein layer. In X-ray reflection studies, we observed that the lysozyme molecules initially adsorbed on the air-water interface have a flat unfolded structure as previously reported in the salt-free solution. In contrast, in the concentrated salt solutions, the lysozyme molecules begin to refold during adsorption. This protein refolding as a result of protein-protein rearrangements may be a precursor phenomenon of crystallization. The refolding is most significant for Cl(-), which is a good crystallization agent, whereas it is less observed for the strongly hydrated F(-). It is widely known in the bulk state that kosmotropic anions tend to precipitate proteins but at the same time stabilize proteins against denaturing. On the other hand, at the air-water interface where adsorbed proteins usually unfold, we observed chaotropic anions strongly bound to proteins that reduce electrostatic repulsion between protein molecules, and subsequently they induce protein refolding whereas the kosmotropic anions do not.

Extended X-ray Absorption Fine Structure (EXAFS) Measurements on Alkali Metal Superatoms of Ta-Atom-Encapsulated Si16 Cage.

The silicon cage nanoclusters encapsulating a tantalum atom, termed Ta@Si16, exhibit characteristics of alkali metal "superatoms (SAs)". Despite this conceptual framework, the precise structures of Ta@Si16 and Ta@Si16+ remain unclear in quantum calculations due to three energetically close structural isomers: C3v, Td, and D4d structures. To identify the geometrical structure of Ta@Si16 SAs, structural analysis was conducted using extended X-ray absorption fine structure (EXAFS) with a high-intensity monochromatic X-ray source, keeping anaerobic conditions. Focusing on "superordered" films, which constitute amorphous thin films composed solely of Ta@Si16 SAs, this analysis preserved locally ordered structures. Spectral comparisons between experimental and simulated Ta L3-edge EXAFS unveil that Ta@Si16 SAs on a substrate adopt a C3v-derived structure, while Si K-edge EXAFS introduces spectral ambiguity in structural identifications, attributed to both intracluster and intercluster scatterings. These findings underscore the significance of locally ordered structure analyses in understanding and characterizing novel nanoscale materials.

First synthesis of RuSn solid-solution alloy nanoparticles and their enhanced hydrogen evolution reaction activity.

Solid-solution alloys based on platinum group metals and p-block metals have attracted much attention due to their promising potential as materials with a continuously fine-tunable electronic structure. Here, we report on the first synthesis of novel solid-solution RuSn alloy nanoparticles (NPs) by electrochemical cyclic voltammetry sweeping of RuSn@SnOx NPs. High-angle annular dark-field scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy maps confirmed the random and homogeneous distribution of Ru and Sn elements in the alloy NPs. Compared with monometallic Ru NPs, the RuSn alloy NPs showed improved hydrogen evolution reaction (HER) performance. The overpotentials of Ru0.94Sn0.06 NPs/C and Ru0.87Sn0.13 NPs/C to achieve a current density of 10 mA cm-2 were 43.41 and 33.19 mV, respectively, which are lower than those of monometallic Ru NPs/C (53.53 mV) and commercial Pt NPs/C (55.77 mV). The valence-band structures of the NPs investigated by hard X-ray photoelectron spectroscopy demonstrated that the d-band centre of RuSn NPs shifted downward compared with that of Ru NPs. X-ray photoelectron spectroscopy and X-ray absorption near-edge structure analyses indicated that in the RuSn alloy NPs, charge transfer occurs from Sn to Ru, which was considered to result in a downward shift of the d-band centre in RuSn NPs and to regulate the adsorption energy of intermediate Hads effectively, and thus enable the RuSn solid-solution alloy NPs to exhibit excellent HER catalytic properties.

Atom-Selective Analyses Reveal the Structure-Directing Effect of Cs Cation on the Synthesis of Zeolites.

To understand the crystallization mechanism of zeolites, it is important to clarify the detailed role of the structure-directing agent, which is essential for the crystallization of zeolite, interacting with an amorphous aluminosilicate matrix. In this study, to reveal the structure-directing effect, the evolution of the aluminosilicate precursor which causes the nucleation of zeolite is analyzed by the comprehensive approach including atom-selective methods. The results of total and atom-selective pair distribution function analyses and X-ray absorption spectroscopy indicate that a crystalline-like coordination environment gradually forms around Cs cations. This corresponds to the fact that Cs is located at the center of the d8r units in the RHO structure whose unit is unique in this zeolite, and a similar tendency is also confirmed in the ANA system. The results collectively support the conventional hypothesis that the formation of the crystalline-like structure before the apparent nucleation of the zeolite.

Underpinning the use of indium as a neutron absorbing additive in zirconolite by X-ray absorption spectroscopy.

Indium (In) is a neutron absorbing additive that could feasibly be used to mitigate criticality in ceramic wasteforms containing Pu in the immobilised form, for which zirconolite (nominally CaZrTi2O7) is a candidate host phase. Herein, the solid solutions Ca1-xZr1-xIn2xTi2O7 (0.10 ≤ x ≤ 1.00; air synthesis) and Ca1-xUxZrTi2-2xIn2xO7 (x = 0.05, 0.10; air and argon synthesis) were investigated by conventional solid state sintering at a temperature of 1350 °C maintained for 20 h, with a view to characterise In3+ substitution behaviour in the zirconolite phase across the Ca2+, Zr4+ and Ti4+ sites. When targeting Ca1-xZr1-xIn2xTi2O7, single phase zirconolite-2M was formed at In concentrations of 0.10 ≤ x ≤ 0.20; beyond x ≥ 0.20, a number of secondary In-containing phases were stabilised. Zirconolite-2M remained a constituent of the phase assemblage up to a concentration of x = 0.80, albeit at relatively low concentration beyond x ≥ 0.40. It was not possible to synthesise the In2Ti2O7 end member compound using a solid state route. Analysis of the In K-edge XANES spectra in the single phase zirconolite-2M compounds confirmed that the In inventory was speciated as trivalent In3+, consistent with targeted oxidation state. However, fitting of the EXAFS region using the zirconolite-2M structural model was consistent with In3+ cations accommodated within the Ti4+ site, contrary to the targeted substitution scheme. When deploying U as a surrogate for immobilised Pu in the Ca1-xUxZrTi2-2xIn2xO7 solid solution, it was demonstrated that, for both x = 0.05 and 0.10, In3+ was successfully able to stabilise zirconolite-2M when U was distributed predominantly as both U4+ and average U5+, when synthesised under argon and air, respectively, determined by U L3-edge XANES analysis.

Influence of Grain Boundary Scattering on the Field-Effect Mobility of Solid-Phase Crystallized Hydrogenated Polycrystalline In2O3 (In2O3:H).

Hydrogenated polycrystalline In2O3 (In2O3:H) thin-film transistors (TFTs) fabricated via the low-temperature solid-phase crystallization (SPC) process with a field-effect mobility (µFE) exceeding 100 cm2 V-1 s-1 are promising candidates for future electronics applications. In this study, we investigated the effects of the SPC temperature of Ar + O2 + H2-sputtered In2O3:H films on the electron transport properties of In2O3:H TFTs. The In2O3:H TFT with an SPC temperature of 300 °C exhibited the best performance, having the largest µFE of 139.2 cm2 V-1 s-1. In contrast, the µFE was slightly degraded with increasing SPC temperature (400 °C and higher). Extended X-ray absorption fine structure analysis revealed that the medium-range ordering in the In2O3:H network was further improved by annealing up to 600 °C, while a large amount of H2O was desorbed from the In2O3:H films at SPC temperatures above 400 °C, resulting in the creation of defects at grain boundaries. The threshold temperature of H2O desorption corresponded well with the carrier transport properties; the µFE of the TFTs started to deteriorate at SPC temperatures of 400 °C and higher. Thus, it was suggested that the hydrogen remaining in the film after SPC plays an important role in the passivation of electron traps, especially for grain boundaries, resulting in an enhancement of the µFE of In2O3:H TFTs.

Multiple valence bands convergence and strong phonon scattering lead to high thermoelectric performance in p-type PbSe.

Thermoelectric generators enable the conversion of waste heat to electricity, which is an effective way to alleviate the global energy crisis. However, the inefficiency of thermoelectric materials is the main obstacle for realizing their widespread applications and thus developing materials with high thermoelectric performance is urgent. Here we show that multiple valence bands and strong phonon scattering can be realized simultaneously in p-type PbSe through the incorporation of AgInSe2. The multiple valleys enable large weighted mobility, indicating enhanced electrical properties. Abundant nano-scale precipitates and dislocations result in strong phonon scattering and thus ultralow lattice thermal conductivity. Consequently, we achieve an exceptional ZT of ~ 1.9 at 873 K in p-type PbSe. This work demonstrates that a combination of band manipulation and microstructure engineering can be realized by tuning the composition, which is expected to be a general strategy for improving the thermoelectric performance in bulk materials.

Binary dopant segregation enables hematite-based heterostructures for highly efficient solar H2O2 synthesis.

Dopant segregation, frequently observed in ionic oxides, is useful for engineering materials and devices. However, due to the poor driving force for ion migration and/or the presence of substantial grain boundaries, dopants are mostly confined within a nanoscale region. Herein, we demonstrate that core-shell heterostructures are formed by oriented self-segregation using one-step thermal annealing of metal-doped hematite mesocrystals at relatively low temperatures in air. The sintering of highly ordered interfaces between the nanocrystal subunits inside the mesocrystal eliminates grain boundaries, leaving numerous oxygen vacancies in the bulk. This results in the efficient segregation of dopants (~90%) on the external surface, which forms their oxide overlayers. The optimized photoanode based on hematite mesocrystals with oxide overlayers containing Sn and Ti dopants realises high activity (~0.8 µmol min-1 cm-2) and selectivity (~90%) for photoelectrochemical H2O2 production, which provides a wide range of application for the proposed concept.

An X-ray absorption spectroscopic study on mixed conductive La0.6Sr0.4Co0.8Fe0.2O(3-δ) cathodes. I. Electrical conductivity and electronic structure.

The electrical conduction mechanism of mixed conductive perovskite oxides, La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-δ), for cathode materials of solid oxide fuel cells has been investigated from electronic structural changes during oxygen vacancy formation. La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-δ) was annealed under various oxygen partial pressures p(O(2))s at 1073 K and quenched. Iodometric titration indicated that the oxygen nonstoichiometry of La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-δ) depended on the annealing p(O(2)), with more oxygen vacancies introduced at lower than at higher p(O(2))s. X-Ray absorption spectroscopic measurements were performed at the O K-, Co L-, Fe L-, Co K-, and Fe K-edges. The valence states of the Co and Fe ions were investigated by the X-ray absorption near edge structure (XANES) at the Co and Fe L(III)-edges. While the Fe average valence was almost constant, the valence of the Co ions decreased with oxygen vacancy introduction. The O K-edge XANES spectra indicated that electrons were injected into the Co 3d/O 2p hybridization state with oxygen vacancy introduction. Both absorption edges at the Co and Fe K-edge XANES shifted towards lower energies with oxygen vacancy introduction. The shift at the Co K-edge resulted from the decrease in the Co average valence and that at the Fe K-edge appeared to be caused by changes in the coordination environment around the Fe ions. The total conductivity of La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-δ) decreased with decreasing p(O(2)), due to a decreasing hole concentration.

Examination of structure and optical properties of Ce3+-doped strontium borate glass by regression analysis.

Amorphous materials with non-periodic structures are commonly evaluated based on their chemical composition, which is not always the best parameter to evaluate physical properties, and an alternative parameter more suitable for performance evaluation must be considered. Herein, we quantified various structural and physical properties of Ce-doped strontium borate glasses and studied their correlations by principal component analysis. We found that the density-driven molar volume is suitable for the evaluation of structural data, while chemical composition is better for the evaluation of optical and luminescent data. Furthermore, the borate-rich glasses exhibited a stronger luminescence due to Ce3+, indicating a higher fraction of BO3/2 ring and larger cavity. Moreover, the internal quantum efficiency was found to originate from the local coordination states of the Ce3+ centres, independent of composition or molar volume. The comparison of numerical data of the matrix is useful not only for ensuring the homogenous doping of amorphous materials by activators, but also for determining the origin of physical properties.

Efficient overall water splitting in acid with anisotropic metal nanosheets.

Water is the only available fossil-free source of hydrogen. Splitting water electrochemically is among the most used techniques, however, it accounts for only 4% of global hydrogen production. One of the reasons is the high cost and low performance of catalysts promoting the oxygen evolution reaction (OER). Here, we report a highly efficient catalyst in acid, that is, solid-solution Ru‒Ir nanosized-coral (RuIr-NC) consisting of 3 nm-thick sheets with only 6 at.% Ir. Among OER catalysts, RuIr-NC shows the highest intrinsic activity and stability. A home-made overall water splitting cell using RuIr-NC as both electrodes can reach 10 mA cm-2geo at 1.485 V for 120 h without noticeable degradation, which outperforms known cells. Operando spectroscopy and atomic-resolution electron microscopy indicate that the high-performance results from the ability of the preferentially exposed {0001} facets to resist the formation of dissolvable metal oxides and to transform ephemeral Ru into a long-lived catalyst.

Structural origin of high-density Gd2O3-MoO3-B2O3 glass and low-density ß'-Gd2(MoO4)3 crystal: a study conducted using high-energy x-ray diffraction and EXAFS at high temperatures.

In this study, the short- and medium-range ordering of 21.25Gd2O3-63.75MoO3-15B2O3 glass (GM15B glass) was studied at temperatures ranging from 297 K to above the crystallization temperature. This was achieved using extended x-ray absorption fine structure and high-energy x-ray diffraction analyses to elucidate the structural origin of the higher glass density (d) as compared to that of precipitated crystals, i.e. GM15B glass with d = 4.762 g cm-3 and ß'-Gd2(MoO4)3 crystal with d = 4.555 g cm-3, and the self-powdering phenomenon in GM15B glass. The bond lengths in the short-range order, i.e. Gd-O, Mo-O, and Gd-Mo in GM15B, were extremely similar to those in the ß-phase; Gd-Gd and Mo-Mo bonds in Gd-O-Gd and Mo-O-Mo, respectively, were not found. The distance between the Gd-Gd pairs in Gd-O-Mo-O-Gd in GM15B glass, r(Gd-Gd) = 6.19 Å, was considerably smaller than that in ß-Gd2(MoO4)3 crystals (6.71 Å) in the crystallized glass at 808 K. This indicates that the glass had a more packed structure than did the precipitated crystals. The probable origin of the self-powdering phenomenon in GM15B glass was the large expansion of the structure during crystallization, which is due to the formation of an open structure with long Gd-Gd pairs and varying bond angles.

Condensed Film Formation and Molecular Packing in Cationic Surfactant-Cholesterol and Zwitterionic Surfactant-Cholesterol Systems at the Hexane/Water Interface.

A condensed film formation of surfactants with a charged head group at the oil/water interface was achieved by mixing surfactants of different geometric shapes to control molecular packing at the interface. The adsorbed films of mixed tetradecyltrimethylammonium bromide (C14TAB)-cholesterol (Chol) and tetradecylphosphocholine (C14PC)-Chol systems at the hexane/water interface were examined by interfacial tension and X-ray reflectivity measurements. The interfacial tension versus Chol concentration curves have break points because of the expanded-condensed phase transition of the adsorbed film. A two dimensional (2D) phase diagram, phase diagram of adsorption, indicated that 1:1 mixing in the condensed film is energetically favorable because of stronger mutual interaction between different molecules than between the same ones. The electron density profile normal to the interface manifested that the packing of C14TAB (or C14PC) and Chol molecules is like a 2D solid in the condensed state. As C14TAB and C14PC molecules take a corn shape with a large head group (critical packing parameter: CPP ≈ 1/3) and Chol takes an inverted corn shape with a bulky sterol ring (CPP > 1), the mixing of corn shape and inverted corn shape molecules produces well-ordered packing to promote solid-like molecular packing at the interface by energy gain because of vdW interaction between hydrophobic chains in addition to attractive ion-dipole interaction between head groups. Furthermore, the heterogeneous feature in the adsorbed film of the C14TAB-Chol system is explained by an interplay between contact energy and dipole interaction, which contribute to line tension at the domain boundary.

Periodic Elastic Motion in a Self-Assembled Monolayer under Spontaneous Oscillations of Surface Tension: Molecules in a Scrum Push Back a Marangoni Flow.

Regularly recurring phenomena are a common and important part of life. Such rhythmic behaviors are often seen in nonliving systems under far-from-equilibrium conditions. The study of simple nonliving systems provides clues for improving our understanding of the origin of biological rhythms. Here, we focus on the spontaneous oscillation of surface tension associated with an intermittent Marangoni convective flow generated by two types of surfactants, those that are partially soluble (long chain alcohols) and insoluble (lipids) in water. In this system, we find that the collective motions of two surfactants interact with each other in a systematic manner to control a stable periodic motion: the alcohol molecules (donor) produce a Marangoni flow, and the lipid molecules (acceptor) in a monolayer push the flow back. The shape of the surface tension oscillation can be explained by the viscoelastic properties of the acceptor surfactant, whereas the period of the surface tension oscillation has been explained by the physical properties of the donor surfactant. A recently developed time-resolved X-ray surface scattering technique enables the dynamic structure of the water surface under flow to be determined. We have repeatedly observed that lipid molecules at the air-water interface become regularly oriented normal to the surface at every onset of the Marangoni convective flow.