Mixed Valence State Research Articles

Electronic and magnetic excitations in La3Ni2O7

High-temperature superconductivity was discovered in the pressurized nickelate La3Ni2O7 which has a unique bilayer structure and mixed valence state of nickel. The properties at ambient pressure contain crucial information of the fundamental interactions and bosons mediating superconducting pairing. Here, using X-ray absorption spectroscopy and resonant inelastic X-ray scattering, we identified that Ni 3dx2−y2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${d}_{{x}^{2}-{y}^{2}}$$\\end{document}, Ni 3dz2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${d}_{{z}^{2}}$$\\end{document}, and ligand oxygen 2p orbitals dominate the low-energy physics with a small charge-transfer energy. Well-defined optical-like magnetic excitations soften into quasi-static spin-density-wave ordering, evidencing the strong electronic correlation and rich magnetic properties. Based on an effective Heisenberg spin model, we extract a much stronger inter-layer effective magnetic superexchange than the intra-layer ones and propose two viable magnetic structures. Our findings emphasize that the Ni 3dz2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${d}_{{z}^{2}}$$\\end{document} orbital bonding within the bilayer induces novel electronic and magnetic excitations, setting the stage for further exploration of La3Ni2O7 superconductor.

Catalase-peroxidase StKatG2 from Salinicola tamaricis: a versatile Mn(II) oxidase that decolorizes malachite green

Manganese (Mn) oxidation processes have garnered significant attention recently due to their potential for degrading organic pollutants. These processes are primarily catalyzed by Mn(II) oxidases. Salinicola tamaricis F01, an endophytic bacterium derived from wetland plants, has demonstrated Mn(II)-oxidizing capacity. In this study, a catalase-peroxidase, StKatG2, was cloned and overexpressed in Escherichia coli from the strain F01. The purified recombinant StKatG2 exhibited Mn(II)-oxidizing activity with Km and Kcat values of 2.529 mmol/L and 2.82 min−1, respectively. Optimal catalytic conditions for StKatG2 were observed at pH 7.5 and 55°C, with 45.1% activity retention after an 8-h exposure to 80°C. The biogenic manganese oxides produced by StKatG2 exhibited mixed-valence states with Mn(II), including Mn(III), Mn(IV), and Mn(VII). Furthermore, StKatG2 demonstrated superior decolorization efficiency for malachite green (MG), achieving decolorization rates of 73.38% for 20 mg/L MG and 60.08% for 50 mg/L MG, while degrading MG into 4-(dimethylamino)benzophenone. Therefore, the catalase-peroxidase StKatG2 exhibits multifunctionality in Mn(II)-oxidizing activity and has the potential to serve as an environmentally friendly enzyme for MG removal.

Dimensionally Extending from 1D MX-Chain to Ladder and Nanotube Systems: Structural and Electronic Properties.

Molecular one-dimensional (1D) electron systems have attracted much attention due to their unique electronic state, physical and chemical properties derived from high-aspect-ratio structures. Among 1D materials, mixed-valence halogen-bridged transition-metal chain complexes (MX-chains) based on coordination assemblies are currently of particular interest because their electronic properties, such as mixed-valence state and band gap, can be controlled by substituting components and varying configurations. In particular, chemistry has recently noted that dimensionally extending MX-chains through organic rung ligands can introduce and modulate electronic coupling of metal atoms between chains, i. e., interchain interactions. In this review, for the first time, we highlight the recent progress on MX systems from the viewpoint of dimensionally extending from 1D chain to ladder and nanotube, mainly involving structural design and electronic properties. Overall, dimensional extension can not only tune the electronic properties of MX-chain, but also build the unique platform for studying transport dynamics in confined space, such as proton conduction. Based on these features, we envision that the MX-chain systems provide valuable insights into deep understanding of 1D electron systems, as well as the potential applications such as nanoelectronics.

Structure and properties of mixed valent CeFe2Al8

Temperature dependent magnetic, electrical transport and thermal properties of polycrystalline orthorhombic CeFe2Al8intermetallic compound have been studied along with its isostructural La counterpart, LaFe2Al8. For the cerium compound, low fielddcmagnetization exhibits an antiferromagnetic like ordering (TN) ∼ 4 K. The main feature of the magnetic susceptibility plot is a broad hump spanning a large temperature range, indicating mixed valence of Ce in the compound, in good agreement with reported literature. However, contrary to the reported observations we find that the mixed valence state is very robust and was evident even up to very high magnetic fields (> 2 T). Further, in this work we report 3d core level photoemission spectra of cerium in CeFe2Al8, to understand the valence state of cerium ions in this system. Additionally, from resistivity measurements it is found that, CeFe2Al8is metallic with no indication of any anomaly, till the lowest temperature of measurement. Specific heat measurements show very low value of heat capacity and electronic contribution. The isostructural La analogue, LaFe2Al8compound shows broadness in susceptibility with maxima around 44 K which may be attributed to ordering of Fe moments. The comparison of Ce and La compounds brings out the role of Fe magnetic moments which may be responsible for competing with cerium moments and resulting in the dilution of long-range magnetic order, also contributing to magnetic frustration in CeFe2Al8.

Smaller rare-earth cation and mixed valent Mn incorporation as a dual strategy to enhance ferrimagnetic ordering temperatures in A-site ordered quadruple perovskites, LnCu3Mn1+xTi3-xO12 (Ln = La, Nd; x = 0, 0.3).

High-TC ferro-/ferrimagnetic quadruple perovskites constitute an important class of oxides that has garnered a lot of research attention in recent times, but their synthesis is commonly achieved under high-pressure conditions. Thus, the development of high-TC quadruple perovskites that can be synthesized under ambient pressure can be a key to the above problem. Herein, we report ambient pressure synthesis of a series of new A-site ordered quadruple perovskites, LnCu3Mn1+xTi3-xO12 (Ln = La, Nd; x = 0, 0.3), by coupled aliovalent-cation manipulation in CaCu3Ti4O12. The effect of smaller lanthanide Nd incorporation in place of La has been investigated. Furthermore, 30% mixed valency of Mn per Mn3+ has been introduced in place of Ti4+ following similar strategies adopted to achieve giant magnetoresistive manganites La0.7A0.3MnO3 (A = Ca, Sr, Ba) from LaMnO3. Mn is present in the 3+ state for x = 0 and in a mixed valent state (3+ and 4+) for x = 0.3, whereas Cu exists in the 2+ state in all the compounds. While LaCu3MnTi3O12 and LaCu3Mn1.3Ti2.7O12 show the onset of ferrimagnetic order at ∼60 and 110 K, respectively, the corresponding Nd analogs, NdCu3MnTi3O12 and NdCu3Mn1.3Ti2.7O12, exhibit enhanced TC's of ∼80 and 140 K, respectively. This work reveals an effective strategy of mixed-valent Mn incorporation in the B-sublattice and smaller rare-earth cation incorporation to achieve higher ferrimagnetic ordering temperatures in quadruple perovskites.

Highly efficient bimetallic counter cations-based tungsten bronzes electrocatalysts developed for sustainable oxygen evolution in acidic solution

This study involves the designing of monophosphate tungsten bronzes (MPTBs) with a combination of earth-abundant Al and Ni counter cations synthesized via the solution combustion as robust, highly efficient electrocatalysts for oxygen evolution reaction (OER) in 1.0 M H2SO4 solution. A series of mixed Al and Ni counter cations-based MPTBs was prepared at different temperatures and characterized with various sophisticated techniques concerning their compositions, morphologies, microstates, and electronic states. The catalyst with Al/Ni ratio of 1:3 of tetragonal cube-shaped MPTB calcined at 700 °C ((Al1/3,Ni)-MPTB7) exhibited an extraordinary OER performance with a larger electrochemically active surface area, almost zero onset overpotential (η), and a lower solar cell-equivalent η (i.e., at 10 mA cm−2) of 199 mV that is lower than that obtained with the state-of-the-art RuO2 catalyst. A progressive enhancement of the performance of the catalysts was noticed for a 12 h OER run, ensuring the robustness of the materials developed for a long-term application. The mixed valency states of tungsten (W), i.e., W5+/W6+ states, along with higher oxygen vacancies of (Al1/3,Ni)-MPTB7 are evaluated to tender suitably oriented active sites for effective adsorption of H2O during the OER. A substantial increase in oxygen vacancies and W5+ state, particularly the W5+4f7/2 state in the catalysts, resulted from a spin-exchange phenomenon during a long-term OER is associated with OER catalytic enhancement. The thus-developed acid-stable, robust MPTBs with mixed Al and Ni counter cations would be an alternative to the pricy noble metal counterparts used in clean energy water splitting technology.

Magnetite Survivability and Non‐Stoichiometric Magnetite Formation in Presence of Oxyhalogen Brines on Mars

AbstractThe mixed Fe(II)/Fe(III) mineral magnetite [Fe3O4] of various stoichiometric and non‐stoichiometric compositions have been reported in Martian soils and rocks by several rover missions. Magnetite is an important paleomagnetic indicator mineral and can serve as a ‘biogeobattery’ as a consequence of its magnetic properties and the mixed valence state of iron in its structure. Here, we assess the extent of oxidative weathering of magnetite in presence of chlorate and bromate containing solutions that are likely important oxidants on Mars. Oxyhalogen species, chlorate and bromate, produced non‐stoichiometric magnetite [Fe(II)/Fe(III) < 0.5] in Mars‐relevant, near‐neutral pH fluids; no other ferric minerals were produced. The same results were observed in highly acidic fluids with or without oxyhalogens. Owing to its resistance to extensive oxidation, magnetite can serve as an important archive of geochemical, paleomagnetic, and astrobiological information in samples that will be returned by the Mars Sample Return mission.

High-Valence Mn MOF Inspired by Laccase Mediators Enables Versatile Nature-Mimicking Catalysis.

In nature, active Mn3+ -ligand complexes produced by laccase catalyzed oxidation can act as the low-molecular mass, diffusible redox mediators to oxidize the phenolic substrates overcoming the limitations of natural enzymes. Learning from the metal-ligand coordination of natural functional units, high-valence Mn metal-organic framework (Mn MOF) is constructed to simulate the catalysis in natural mediator system. Benefiting from the characteristics of nanoscale size, rich metal coordination unsaturated sites, and mixed valence state dominated by Mn(III), Nano Mn(III)-TP exhibits superior laccase-mimicking activity, whose Vmax (maximal reaction rate) is much higher than that of natural laccase. Referring to natural systems, relevant free radical experiments prove that the material induces the production of active oxygen species with the assistance of carboxylic acid, and active oxygen species further oxidize phenolic substrates. Based on its robust performances, the primary oxidative degradation of an emerging pollutant triclosan (TCS) is creatively applied, an important antiasthmatic medicine terbutaline sulfate (TBT) detection, and the synthesis of non-toxic and black near-natural dyes for dyeing. By simulating the essential mediators of natural enzymatic catalysis, an Mn MOF-based material that demonstrates multiple novel applications is successfully developed, which introduces a new reliable strategy for achieving versatile nature-mimicking catalysis.

A comparative study of influence of isovalent and aliovalent A-site substitutions on the structural, magnetic, and dielectric properties of Sr2CrMoO6 double perovskites

We report on a comparative study of the structural, magnetic, and dielectric and properties of isovalent and aliovalent A-site substituted Sr2-xAxCrMoO6 (A = Ca, x = 0.0, 0.1, 0.3, 0.5, 0.7, 0.8, 1.0; A = K, La only x = 0.5) double perovskites, which were synthesized via sol-gel process. X-ray diffraction patterns and Rietveld refinements demonstrated that all the Sr2-xAxCrMoO6 powders crystallized in a cubic crystal structure with space group of Fm3‾m. SEM images revealed that the Sr2-xAxCrMoO6 powders exhibited a spherical morphology. Their chemical compositions were determined by quantitative energy dispersive X-ray spectroscopy, which were close to the nominal values. FTIR spectra analyses verified the presence of (Cr, Mo)O6 octahedra in these powders. XPS spectra validated the existence of Sr2+, K+, Ca2+, La3+, and Cr3+ ions in the powders, and oxygen existed in the forms of lattice oxygen and absorbed oxygen respectively, whereas Mo element had a mixed chemical valence state of Mo4+ and Mo6+. The Sr2CrMoO6 (SCMO) powders had a saturation magnetization (MS) of 0.016 μB/f.u. at 2 K, magnetic Curie temperature (TC) of 337 K, and irreversibility temperature (Tirr) of 329 K where the zero-field cooled (ZFC) and field-cooled (FC) magnetization (MZFC and MFC, respectively) curves became bifurcated. A spin-glass behavior was observed at temperature (TB) of 81 K. Both Tirr and TB shifted towards low temperature with increasing the external magnetic field. In addition, the MZFC and MFC curves became almost overlapped under the external field of 50 kOe, and the spin-glass behavior disappeared. The M-H data demonstrated that both isovalent and aliovalent A-site substitutions could improve the magnetic properties and B-site ordering degree (η) of the SCMO powders. However, isovalent Ca-substitution exhibited more significant enhanced effect on the magnetic properties in comparison with the aliovalent A-site substitutions either by K- or La-substitution. Among the isovalent Ca-substituted Sr2-xCaxCrMoO6 (x = 0.1–1.0) powders, Sr1.2Ca0.8CrMoO6 sample had a maximum MS value of 0.64 μB/f.u. at 2 K, over 30 times enhancement of that of the pristine SCMO powders. The Sr2-xAxCrMoO6 ceramics exhibit a strong frequency dependent dielectric behavior, which can be well interpreted by Maxwell-Wagner relaxation model. The anomalous dielectric relaxor behavior of the SCMO ceramics observed at 260 K was ascribed to the jumping of the electrons trapped in a shallower energy level created by oxygen vacancies. The dielectric constant of the isovalent Ca-substituted Sr1.5Ca0.5CrMoO6 samples was 30 times larger than that of the pristine SCMO samples. Our present results demonstrate that isovalent Ca-substitution at A-site could improve the magnetic and dielectric properties of the sol-gel derived SCMO double perovskite oxides, which have potential applications in the fields of spintronic devices and dielectric devices.

Exploring the role of transition metal ions doping on the optical, magnetic and energy storage properties of Bi0.96Eu0.04FeO3 nanoparticles

Bismuth ferrite has been quite extensively studied because of its unique multiferroic properties. The introduction of dopants strategically at the ‘A’ and ‘B’ sites has been known to improve the multiferroic properties of bismuth ferrite. This study focuses on the detailed investigation of the structural, morphological, optical, magnetic, and electrochemical properties of sol-gel synthesized bismuth ferrite as well as Bi0.96Eu0.04Fe0.95M0.05O3(M=Mn, Cu, Co, Zn) nanoparticles. The crystal structure and morphological analysis are done using XRD, Rietveld refinement, and FESEM. The XRD analysis and Rietveld Refinement have confirmed a structural transition to the orthorhombic phase upon simultaneous co-doping of ‘Eu’ and ‘M’(M= Mn, Cu, Co, Zn) ions at the ‘A’ and ‘B’ sites respectively. The evidence of different ratios of mixed valence states of ‘Fe’ and oxygen vacancies in the co-doped nanoparticles dictates the enhanced magnetic properties. There is a significant decrease in the band-gap of co-doped nanoparticles obtained from Tauc’s plot, with the lowest achieved band-gap of 1.8 eV in the case of ‘Eu’ and ‘Mn’ doped nanoparticles. Room-temperature M-H loops have recorded an increase in the value of maximum magnetization from 0.1 emu/g in case of pristine bismuth ferrite to 0.79 emu/g for ‘Eu’ and ‘Co’ doped bismuth ferrite nanoparticles. The unsaturated loops, however, have confirmed the presence of anti-ferromagnetic component along with the ferromagnetic part. The electrochemical studies have shown superior specific capacitance in co-doped bismuth ferrite, with the maximum specific capacitance of 273 F/g for ‘Eu’ and ‘Zn’ doped bismuth ferrite. It has also shown remarkable capacitive retention of 84.8 % after 5000 cycles at 10 A/g.

Modulating the structural and electrical properties of SrFeO3–δ by a-site alkali metal ion doping

The electrical properties of perovskite structured SrFeO3–δ can be modulated by A site doping. The present work focuses on the influence of concentration and ionic radii of alkali metal cation on the structural and electrical properties of Sr1–xAxFeO3–δ (A = Ca, Ba and x = 0, 0.25, 0.50, 0.75). The x-ray diffraction studies confirm the phase change from cubic to orthorhombic with Ca content while orthorhombic to cubic structural translation was observed with Ba concentration. A lattice contraction and expansion were observed for doping depending on the ionic radii of dopant cation. The x-ray photoelectron spectroscopy results indicate the presence of Fe in mixed valence state of +2, +3, +4 state and adsorbed oxygen content was found to be higher upon Ba doping than that of Ca. A maximum conductivity of 1.82 × 10−3 S cm−1 (x = 0.25) and 5.31 × 10−3 S cm−1 (x = 0.5) was observed at 800 °C for Ca and Ba doped samples, respectively, one order higher than the base SrFeO3–δ .Thus, our results emphasise the importance of dopant addition on tailoring the electrode properties for SOFC application.

Anion-intercalation pseudocapacitance in oxygen vacancy-rich spinel-perovskite NiFe2O4-LaFeO3 nanocomposite for high energy density asymmetric supercapacitor application

Oxide nanomaterials have attracted significant attention as energy storage materials. The combination of spinel-perovskite oxides as nanocomposites creates dense oxygen vacancies (VO) at the hetero-interface. VO present in the complex oxides are indispensable for energy conversion applications. Herein, we demonstrated the one pot synthesis of spinel-perovskite NiFe2O4-xLaFeO3 nanocomposite and investigated the phase formation using variable temperature powder X-ray diffraction of the gel precursor. The role of oxygen-vacancy mediated tuneable redox transitions in NiFe2O4-xLaFeO3 nanocomposite has been understood. The anion-intercalation-based pseudocapacitance and the oxygen intercalation have been exploited for high-performance electrochemical energy storage. The NiFe2O4–2LaFeO3 exhibited a high specific capacity of 652 C g−1 at a current density of 2 A g−1. The fabricated NiFe2O4–2LaFeO3||NiCo2O4 asymmetric supercapacitor device (ASC) exhibited excellent cyclability over 20,000 cycles with superior capacity retention and high Coulombic efficiency (92 %) and achieved a high energy density of 42.5 Wh kg−1 at a power density of 1500 W kg−1. The presence of VO and the mixed-valence states of Fe2+/3+ were confirmed by XPS-depth profiling. The tuneable redox transition of Fe2+/3+ and VO contribute to the higher pseudocapacitance response.

From LaCrO3 towards LaCr0.2Mn0.2Fe0.2Al0.2Ga0.2O3 high-entropy ceramic compound: Crystal structure, dielectric and magnetic properties

A group of five perovskite-type ceramic systems was designed by solid-state reaction, increasing the configurational entropy, ΔSconf at the B-site, going from low and medium to finally reaching a high-entropy system. Chemical elements, crystal structure, and microstructure characterization, as well as the dielectric and magnetic properties, are discussed from the single phase LaCrO3 towards a continuous equiatomic multicomponent LaCr0.2Mn0.2Fe0.2Al0.2Ga0.2O3 ceramic compounds. Through a combination of structural analysis and XPS spectroscopy study, it is found that not only the configurational entropy ∆Sconf term, but also the enthalpy of mixing, ΔHmix through of arising of the coexistence of mixed valence state, oxygen vacancies, and local octahedral distortions lead to the stabilization of the single phase in equimolar multicomponent perovskite systems. The arising of Cr3+/Cr6+ and Mn3+/Mn2+ mixed valence state drives the AC electric conductivity through the presence of two kinds of charge carriers, small polarons and oxygen vacancies in LCM, LCMF, LCMFA, and LCMFAG ceramic compounds. The occurrence of these two classes of charge carriers progressively increases the AC electric conductivity at room and high temperatures for each ceramic compound, being higher for the LCMFA entropy compound, making it a potential candidate for solid oxide fuel cell (SOFC) applications. As expected, the increases of compositional random cations display rich magnetic properties arising from competing magnetic interactions driven by the sublattice of Cr, Mn, and Fe magnetic ions. The resulting ΔSconf increase leads to a Griffith-like phase. The results also show that not only the ferromagnetic clusters of the LaMnO3 (AxFz) sublattice but also the weak ferromagnetism associated with the LaCrO3 (GxFz), and LaFeO3 (GxFz) sublattices play a predominant role in the formation of the Griffiths-like phase in the low, medium and high-entropy ceramic systems.

Pleiotropy of biomineralized bacterial outer membrane vesicles in modulating immune systems for liver cancer therapy

The immune landscape of late-stage liver cancer is featured by severe immunosuppression that is characterized by poor immunogenicity, T-cell exhaustion, and infiltration of a large number of immunosuppressive cells, leading to compromised therapeutic efficacy of mainstream immunotherapies. Herein, we developed a pleiotropic immune cell mobilization strategy to modulate immune systems for immunosuppressive liver cancer therapy. In this study, immunogenic bacteria-derived outer membrane vesicles (OMVs) were exploited as a vector to deposit Cu and Mn with mixed valence states via one-step biomineralization, followed by platelet membrane camouflage, which are denoted as OPCM. Mechanistically, the pleiotropic OPCM possesses POD, CAT, and GPX-like activities, thereby achieving cGAS-STING activation, immunogenic ferroptosis, and tumor hypoxia alleviation, ultimately leading to initiation of the cancer immunity cycle, modulation of both innate and adaptive immune system, and reversion of immunosuppression. Notably, the combination with typical αPD-L1 treatment augmented the tumor suppression effect by amplifying the intensity of ferroptosis due to IFN-γ secretion by activated T cells. Overall, the metal biomineralized OPCMs in combination with αPD-L1 formed a closed-loop therapy that cycles from immunotherapy and ferroptosis therapy, providing new insights for treating immunosuppressive liver cancer.

Modulated assembly and structural diversity of heterometallic Sn-Ti oxo clusters from inorganic tin precursors.

Through modulating the multidentate ligands, solvent environments, and inorganic tin precursors during the synthesis processes, we have successfully prepared a series of unprecedented heterometallic Sn-Ti oxo clusters with structural diversity and different physiochemical attributes. Initially, two Sn6Ti10 clusters were synthesized using trimethylolpropane as a structure-oriented ligand and SnCl4·5H2O as a tin source. Then, when a larger pentadentate ligand di(trimethylolpropane) was used instead of trimethylolpropane and aprotic acetonitrile solvent was introduced into the reaction system, four low-nuclearity Sn-Ti oxo clusters were discovered, including two Sn1Ti1, one Sn2Ti2 and one Sn2Ti6. Finally, two mixed-valence state clusters, SnII4SnIV2TiIV14 and SnII4SnIV4TiIV20, were obtained by transforming the tin precursor from SnCl4·5H2O to SnCl2·2H2O and adjusting the acetonitrile solution with trace acetic acid/formic acid. Sn8Ti20 is the highest-nuclearity heterometallic Sn-Ti oxo cluster to date. Moreover, comparative electrocatalytic CO2 reduction experiments were carried out, and it was concluded that the Sn8Ti20-decorated electrode showed the most satisfactory performance due to the influence of mixed-valence states of the Sn atoms and the charging effects provided by 20 Ti4+ ions. This study presents important guiding significance for the design, synthesis and application optimization of functional heterometallic nanoclusters.

Mixed-valence state in the dilute-impurity regime of La-substituted SmB6

Homogeneous mixed-valence (MV) behaviour is one of the most intriguing phenomena of f-electron systems. Despite extensive efforts, a fundamental aspect which remains unsettled is the experimental determination of the limiting cases for which MV emerges. Here we address this question for SmB6, a prototypical MV system characterized by two nearly-degenerate Sm2+ and Sm3+ configurations. By combining angle-resolved photoemission spectroscopy (ARPES) and x-ray absorption spectroscopy (XAS), we track the evolution of the mean Sm valence, vSm, in the SmxLa1−xB6 series. Upon substitution of Sm ions with trivalent La, we observe a linear decrease of valence fluctuations to an almost complete suppression at x = 0.2, with vSm ~ 2; surprisingly, by further reducing x, a re-entrant increase of vSm develops, approaching the value of vimp ~ 2.35 in the dilute-impurity limit. Such behaviour departs from a monotonic evolution of vSm across the whole series, as well as from the expectation of its convergence to an integer value for x → 0. Our ARPES and XAS results, complemented by a phenomenological model, demonstrate an unconventional evolution of the MV character in the SmxLa1−xB6 series, paving the way to further theoretical and experimental considerations on the concept of MV itself, and its influence on the macroscopic properties of rare-earth compounds in the dilute-to-intermediate impurity regime.

MoⅣ boosted carrier density of MoO3-X for surface-enhanced Raman spectroscopy

Molybdenum oxides (MoO3-X) with the same surface plasmon resonance (SPR) effect as Au/Ag, and occupies an irreplaceable value in SERS detections. MoO3-X SERS substrates with oxygen-rich defects tend to show better SERS performance, but the preparation and characterization of tunable O defects remain challenging. It cannot be ignored that the oxidation state of metal cations is also influenced by O defects. Here, a series of MoO3-X SERS sensors with regulable Mo valence state were fabricated using magnetron sputtering technology. By changing the Mo sputtering power and the O2/Ar2 ratio, the Mo/O element ratio of the substrate can be easily regulated to readjust the O defects. The X-ray Photoelectron Spectroscopy (XPS) and Raman spectra were performed to investigate the change and related relationship between Mo mixed valence state and SERS sensitivity. The abundant incompletely coordinated electrons produced by low valence MoⅣ act as free carriers, increasing the free carrier density of MoO3-X substrates, which is beneficial for the SERS effect. It has also been proven by Hall effect measurement. The SERS measurement shows that the enhancement factor (EF) reached 3.70 × 105, which is exceedingly close to Au/Ag. The MoO2.5 substrate also exhibited a repeatable and consistent response, high stability, and repeatability, which proves the splendid application potential in complex environments.

Impeding conduction by breaking the charge carrier hopping in charge-ordered perovskite BaBiO3 ([formula omitted]): Experimental and theoretical electronic structural correlations

BaBiO3 (BBO), a charge-ordered perovskite with mixed-valent states of Bi (Bi3+ and Bi5+), is known for its charge density wave (CDW) semiconducting and topological insulating properties. BBO has been extensively investigated for its superconducting, electrical, and photocatalytic properties. The present study aims to understand the alterations in the CDW and electronic properties of BaBi0.53+Bi0.55+O3 by valence-selective substitution of Bi3+ and Bi5+ with La3+ and Nb5+, respectively, in the solid solutions BaBi0.5−x3+LaxBi0.55+O3 and BaBi0.53+Bi0.5−y5+NbyO3 (x = y = 0.0, 0.1, 0.3, and 0.5). The samples synthesized via high-temperature solid-state reaction method were characterized by powder X-ray diffraction and various spectroscopic techniques (FT-IR, Laser Raman, EPR, XPS, and UPS). Impedance analysis revealed an upsurge in total impedance with the substitution of Bi3+/Bi5+ by La3+/Nb5+ indicating the blocking of electron/hole hopping by disruption of the charge ordering of redox pair Bi3+ and Bi5+. The valence-selective substitution of Bi3+/Bi5+ in BaBiO3 resulted in an alteration of the electronic structure and changes in the bandwidth of BaBi0.5−x3+LaxBi0.55+O3 and BaBi0.53+Bi0.5−y5+NbyO3 (x = y = 0.0, 0.1, 0.3, and 0.5) solid solutions, which were confirmed by both theoretical density of states (DOS) calculations and experimental ultraviolet photoelectron spectroscopic (UPS) studies.

Co(III)–Co(II)–Co(III) edge-sharing trinuclear complexes having the doubly methoxido-bridged core bridged by acetato ligand

Two trinuclear cobalt complexes with the edge-sharing linear-type framework having benzylbis(2-pyridylmethyl)amine (bbpma), [{CoIII(bbpma)(μ-O2CCH3)(μ-OCH3)2}2CoII](X)2 (X=ClO4; [1](ClO4)2, X =PF6; [1](PF6)2), and one corresponding complex having ethylbis(2-pyridylmethyl)amine (ebpma), [{CoIII(ebpma)(μ-O2CCH3)(μ-OCH3)2}2CoII](PF6)2 ([2](PF6)2), were synthesized and the crystallographic and electronic structures were investigated. X-ray crystallography and magnetic measurements suggested that [1](PF6)2 and [2](PF6)2 were in the mixed-valent state and the mixed-spin state of Co(III)–Co(II)–Co(III) (LS-HS-LS), in which the electron spins were much localized on the central Co(II).

Synergistic degradation of p-nitrophenol using peroxymonosulfate activated with a bimetallic Mn3O4–Cu2O catalyst: Investigation of strong interactions between metal oxides

The use of efficient, eco-friendly catalysts is essential for activating peroxymonosulfate (PMS) to degrade organic contaminants in aqueous media. In this study, we developed a novel approach to fabricating bimetallic MnCu catalysts (Mn:Cu molar ratios: 10:1, 5:1, 3:1, and 2:1) comprising tetragonal Mn3O4 and cubic Cu2O. MnCu-5:1 exhibited superior catalytic activity for the degradation of p-nitrophenol (PNP) using PMS because of the synergistic interplay between Mn and Cu. Experimental and density functional theory (DFT) calculation data revealed that the mixed valence states and strong interactions between Mn and Cu in the MnCu-5:1 system increased the electron transfer efficiency and promoted electron transfer to PMS. The results of quenching experiments elucidated a primary radical mechanism and minor nonradical pathway for the PNP degradation over the MnCu-5:1/PMS system. DFT calculations confirmed a relatively high adsorption energy of the Mn3O4–Cu2O (MnCu) composite, indicating enhanced catalytic performance. The superior reactivity of the composite was verified by analyzing its density of states and electrostatic difference potential. Our findings offer fresh perspectives for harnessing the synergistic potential of less toxic mixed metal oxides for controlling catalytic properties and help achieve a better understanding of the activation mechanism for contaminant degradation over MnCu catalysts.