Towards direct laser writing of actively tuneable three-dimensional photonic crystals

3D printing and actively switchable redox‐active oligo(aniline)‐based materials are combined to create novel tuneable 3D photonic materials. By a direct laser writing process, switchable functional structures with submicrometer features are fabricated. Reversible changes in the refractive index of the written materials are generated with negligible size changes

Catalysis enabled synthesis, structures, and reactivities of fluorinated S8-corona[n]arenes (n = 8–12)

Previously inaccessible large S8-corona[n]arene macrocycles (n = 8–12) with alternating aryl and 1,4-C6F4 subunits are easily prepared on up to gram scales, without the need for chromatography (up to 45% yield, 10 different examples) through new high acceleration SNAr substitution protocols (catalytic NR4F in pyridine, R = H, Me, Bu). Macrocycle size and functionality are tunable by precursor and catalyst selection. Equivalent simple NR4F catalysis allows facile late-stage SNAr difunctionalisation of the ring C6F4 units with thiols (8 derivatives, typically 95+% yields) providing two-step access to highly functionalised fluoromacrocycle libraries. Macrocycle host binding supports fluoroaryl catalytic activation through contact ion pair binding of NR4F and solvent inclusion. In the solid-state, solvent inclusion also intimately controls macrocycle conformation and fluorine–fluorine interactions leading to spontaneous self-assembly into infinite columns with honeycomb-like lattices

A Soluble ‘Ba(Ni-ett)’ (ett = 1,1,2,2-Ethenetetrathiolate) Derived Thermoelectric Material

We describe the synthesis and characterisation of the first of a new class of soluble ladder oligomeric thermoelectric material based on previously unutilised ethene-1,1,2,2-tetrasulfonic acid. Reaction of Ba(OH)2 and propionic acid at a 1:1 stoichiometry leads to the formation of the previously unrecognised soluble [Ba(OH)(O2CEt)]⋅H2O. The latter when used to hydrolyse 1,3,4,6-tetrathiapentalene-2,5-dione (TPD), in the presence of NiCl2, forms a new material whose elemental composition is in accord with the formula [(EtCO2Ba)4Ni8{(O3S)2C = C(SO3)2}5]⋅22H2O (4). Compound 4 can be pressed into pellets, drop-cast as DMSO solutions or ink-jet printed (down to sub-mm resolutions). While its room temperature thermoelectric properties are modest (σmax 0.04 S cm−1 and Seebeck coefficient, αmax − 25.8 μV K−1) we introduce a versatile new oligomeric material that opens new possible synthetic routes for n-type thermoelectrics

Bi2Se3 interlayer treatments affecting the Y3Fe5O12 (YIG) platinum spin Seebeck effect

In this work, we present a method to enhance the longitudinal spin Seebeck effect at platinum/yttrium iron garnet (Pt/YIG) interfaces. The introduction of a partial interlayer of bismuth selenide (Bi2Se3, 2.5% surface coverage) interfaces significantly increases (by ∼380%–690%) the spin Seebeck coefficient over equivalent Pt/YIG control devices. Optimal devices are prepared by transferring Bi2Se3 nanoribbons, prepared under anaerobic conditions, onto the YIG (111) chips followed by rapid over-coating with Pt. The deposited Pt/Bi2Se3 nanoribbon/YIG assembly is characterized by scanning electron microscope. The expected elemental compositions of Bi2Se3 and YIG are confirmed by energy dispersive x-ray analysis. A spin Seebeck coefficient of 0.34–0.62 μV/K for Pt/Bi2Se3/YIG is attained for our devices, compared to just 0.09 μV/K for Pt/YIG controls at a 12 K thermal gradient and a magnetic field swept from −50 to +50 mT. Superconducting quantum interference device magnetometer studies indicate that the magnetic moment of Pt/Bi2Se3/YIG treated chips is increased by ∼4% vs control Pt/YIG chips (i.e., a significant increase vs the ±0.06% chip mass reproducibility). Increased surface magnetization is also detected in magnetic force microscope studies of Pt/Bi2Se3/YIG, suggesting that the enhancement of spin injection is associated with the presence of Bi2Se3 nanoribbons

Phase-Modified Strongly Coupled δ/ε-MnO₂ Homojunction Cathode for Kinetics-Enhanced Zinc-Ion Batteries

Rechargeable Zn-MnO2 batteries using mild water electrolytes have garnered significant interest owing to their impressive theoretical energy density and eco-friendly characteristics. However, MnO2 suffers from huge structural changes during the cycles, resulting in very poor stability at high charge–discharge depths. Briefly, the above problems are caused by slow kinetic processes and the dissolution of Mn atoms in the cycles. In this paper, a 2D homojunction electrode material (δ/ε-MnO2) based on δ-MnO2 and ε-MnO2 has been prepared by a two-step electrochemical deposition method. According to the DFT calculations, the charge transfer and bonding between interfaces result in the generation of electronic states near the Fermi surface, giving δ/ε-MnO2 a more continuous distribution of electron states and better conductivity, which is conducive to the rapid insertion/extraction of Zn2+ and H+. Moreover, the strongly coupled Mn–O–Mn interfacial bond can effectively impede dissolution of Mn atoms and thus maintain the structural integrity of δ/ε-MnO2 during the cycles. Accordingly, the δ/ε-MnO2 cathode exhibits high capacity (383 mAh g–1 at 0.1 A g–1), superior rate performance (150 mAh g–1 at 5 A g–1), and excellent cycling stability over 2000 cycles (91.3% at 3 A g–1). Profoundly, this unique homojunction provides a novel paradigm for reasonable selection of different components