Orthorhombic Ti2O3: A Polymorph‐Dependent Narrow‐Bandgap Ferromagnetic Oxide

Magnetic semiconductors are highly sought in spintronics, which allow not only the control of charge carriers like in traditional electronics, but also the control of spin states. However, almost all known magnetic semiconductors are featured with bandgaps larger than 1 eV, which limits their applications in long‐wavelength regimes. In this work, the discovery of orthorhombic‐structured Ti₂O₃ films is reported as a unique narrow‐bandgap (≈0.1 eV) ferromagnetic oxide semiconductor. In contrast, the well‐known corundum‐structured Ti₂O₃ polymorph has an antiferromagnetic ground state. This comprehensive study on epitaxial Ti₂O₃ thin films reveals strong correlations between structure, electrical, and magnetic properties. The new orthorhombic Ti₂O₃ polymorph is found to be n‐type with a very high electron concentration, while the bulk‐type trigonal‐structured Ti₂O₃ is p‐type. More interestingly, in contrast to the antiferromagnetic ground state of trigonal bulk Ti₂O₃, unexpected ferromagnetism with a transition temperature well above room temperature is observed in the orthorhombic Ti₂O₃, which is confirmed by X‐ray magnetic circular dichroism measurements. Using first‐principles calculations, the ferromagnetism is attributed to a particular type of oxygen vacancies in the orthorhombic Ti₂O₃. The room‐temperature ferromagnetism observed in orthorhombic‐structured Ti₂O₃, demonstrates a new route toward controlling magnetism in epitaxial oxide films through selective stabilization of polymorph phases.     

A 0D Lead‐Free Hybrid Crystal with Ultralow Thermal Conductivity

Organic–inorganic hybrid materials are of significant interest owing to their diverse applications ranging from photovoltaics and electronics to catalysis. Control over the organic and inorganic components offers flexibility through tuning their chemical and physical properties. Herein, it is reported that a new organic–inorganic hybrid, [Mn(C₂H₆OS)₆]I₄, with linear tetraiodide anions exhibit an ultralow thermal conductivity of 0.15 ± 0.01 W m^?1 K^?1 at room temperature, which is among the lowest values reported for organic–inorganic hybrid materials. Interestingly, the hybrid compound has a unique 0D structure, which extends into 3D supramolecular frameworks through nonclassical hydrogen bonding. Phonon band structure calculations reveal that low group velocities and localization of vibrational energy underlie the observed ultralow thermal conductivity, which could serve as a general principle to design novel thermal management materials.     

Unprecedented Surface Plasmon Modes in Monoclinic MoO2 Nanostructures

Developing stable plasmonic materials featuring earth-abundant compositions with continuous band structures, similar to those of typical metals, has received special research interest. Owing to their metal-like behavior, monoclinic MoO₂ nanostructures have been found to support stable and intense surface plasmon (SP) resonances. However, no progress has been made on their energy and spatial distributions over individual nanostructures, nor the origin of their possibly existing specific SP modes. Here, various MoO₂ nanostructures are designed via polydopamine chemistry and managed to visualize multiple longitudinal and transversal SP modes supported by the monoclinic MoO₂, along with intrinsic interband transitions, using scanning transmission electron microscopy coupled with ultrahigh-resolution electron energy loss spectroscopy. The identified geometry-dependent SP energies are tuned by either controlling the shape and thickness of MoO₂ nanostructures through their well-designed chemical synthesis, or by altering their length using a developed electron-beam patterning technique. Theoretical calculations reveal that the strong plasmonic behavior of the monoclinic MoO₂ is associated with the abundant delocalized electrons in the Mo d orbitals. This work not only provides a significant improvement in imaging and tailoring SPs of nonconventional metallic nanostructures, but also highlights the potential of MoO₂ nanostructures for micro–nano optical and optoelectronic applications.     

A Laser-Induced Mo2CTx MXene Hybrid Anode for High-Performance Li-Ion Batteries

MXenes, a fast-growing family of two-dimensional (2D) transition metal carbides/nitrides, are promising for electronics and energy storage applications. Mo₂CT_x MXene, in particular, has demonstrated a higher capacity than other MXenes as an anode for Li-ion batteries. Yet, such enhanced capacity is accompanied by slow kinetics and poor cycling stability. Herein, it is revealed that the unstable cycling performance of Mo₂CT_x is attributed to the partial oxidation into MoO_x with structural degradation. A laser-induced Mo₂CT_x/Mo₂C (LS-Mo₂CT_x) hybrid anode has been developed, of which the Mo₂C nanodots boost redox kinetics, and the laser-reduced oxygen content prevents the structural degradation caused by oxidation. Meanwhile, the strong connections between the laser-induced Mo₂C nanodots and Mo₂CT_x nanosheets enhance conductivity and stabilize the structure during charge–discharge cycling. The as-prepared LS-Mo₂CT_x anode exhibits an enhanced capacity of 340 mAh g⁻¹ vs 83 mAh g⁻¹ (for pristine) and an improved cycling stability (capacity retention of 106.2% vs 80.6% for pristine) over 1000 cycles. The laser-induced synthesis approach underlines the potential of MXene-based hybrid materials for high-performance energy storage applications.     

Substrate dependent self-organization of mesoporous cobalt oxide nanowires with remarkable pseudocapacitance

A scheme of current collector dependent self-organization of mesoporous cobalt oxide nanowires has been used to create unique supercapacitor electrodes, with each nanowire making direct contact with the current collector. The fabricated electrodes offer the desired properties of macroporosity to allow facile electrolyte flow, thereby reducing device resistance and nanoporosity with large surface area to allow faster reaction kinetics. Co(3)O(4) nanowires grown on carbon fiber paper collectors self-organize into a brush-like morphology with the nanowires completely surrounding the carbon microfiber cores. In comparison, Co(3)O(4) nanowires grown on planar graphitized carbon paper collectors self-organize into a flower-like morphology. In three electrode configuration, brush-like and flower-like morphologies exhibited specific capacitance values of 1525 and 1199 F/g, respectively, at a constant current density of 1 A/g. In two electrode configuration, the brush-like nanowire morphology resulted in a superior supercapacitor performance with high specific capacitances of 911 F/g at 0.25 A/g and 784 F/g at 40 A/g. In comparison, the flower-like morphology exhibited lower specific capacitance values of 620 F/g at 0.25 A/g and 423 F/g at 40 A/g. The Co(3)O(4) nanowires with brush-like morphology exhibited high values of specific power (71 kW/kg) and specific energy (81 Wh/kg). Maximum energy and power densities calculated for Co(3)O(4) nanowires with flower-like morphology were 55 Wh/kg and 37 kW/kg respectively. Both electrode designs exhibited excellent cycling stability by retaining ～91-94% of their maximum capacitance after 5000 cycles of continuous charge-discharge.