Bottom-up synthesis of 2D layered high-entropy transition metal hydroxides.

Low-dimensional high-entropy materials, such as nanoparticles and two-dimensional (2D) layers, have great potential for catalysis and energy applications. However, it is still challenging to synthesize 2D layered high-entropy materials through a bottom-up soft chemistry method, due to the difficulty of mixing and assembling multiple elements in 2D layers. Here, we report a simple polyol process for the synthesis of a series of 2D layered high-entropy transition metal (Co, Cr, Fe, Mn, Ni, and Zn) hydroxides (HEHs), involving the hydrolysis and inorganic polymerization of metal-containing species in ethylene glycol media. The as-synthesized HEHs demonstrate 2D layered structures with interlayer distances ranging from 0.860 to 0.987 nm and homogeneous elemental distribution of designed equimolar stoichiometry in the layers. These 2D HEHs exhibit a low overpotential of 275 mV at 10 mA cm-2 in a 0.1 M KOH electrolyte for the oxygen evolution reaction. Superparamagnetic spinel-type high-entropy nanoparticles can also be obtained by annealing these HEHs. Our polyol approach creates opportunities for synthesizing low-dimensional high-entropy materials with promising properties and applications.

Useful High-Entropy Source on Spinel Oxides for Gas Detection.

This study aimed to identify a useful high-entropy source for gas detection by spinel oxides that are composed of five cations in nearly equal molar amounts and free of impurities. The sensor responses of the spinel oxides [1# (CoCrFeMnNi)3O4, 2# (CoCrFeMnZn)3O4, 3# (CoCrFeNiZn)3O4, 4# (CoCrMnNiZn)3O4, 5# (CoFeMnNiZn)3O4, and 6# (CrFeMnNiZn)3O4] were evaluated for the test gases (7 ppm NO2, 5000 ppm H2, 3 ppm NH3, and 3 ppm H2S). In response to NO2, 1# and 2# showed p-type behavior while 3-6# showed n-type semiconductor behavior. There are three p-type and one n-type AO structural compositions in AB2O4[AO·B2O3] type spinel, and 1# showed a stable AO composition because cation migration from site B to site A is unlikely. Therefore, it was assumed that 1# exhibited p-type behavior. The p-type behavior of 2# was influenced by Cr oxide ions that were present at the B site and the stable p-type behavior of zinc oxide at the A site. The spinel oxides 3# to 6# exhibited n-type behavior with the other cationic oxides rather than the dominant p-type behavior exhibited by the Zn oxide ions that are stable at the A site. In contrast, the sensor response to the reducing gases H2, NH3, and H2S showed p-type semiconductor behavior, with a particularly selective response to H2S. The sensor responses of the five-element spinel oxides in this study tended to be higher than that of the two-element Ni ferrites and three-element Ni-Zn ferrites reported previously. Additionally, the susceptibility to sulfurization was evaluated using the thermodynamic equilibrium theory for the AO and B2O3 compositions. The oxides of Cr, Fe, and Mn ions in the B2O3 composition did not respond to H2S because they were not sulfurized. The increase in the sensor response due to sulfurization was attributed to the decrease in the depletion layer owing to electron sensitization, as the top surface of the p-type semiconductors, ZnO and NiO, transformed to n-type semiconductors, ZnS and NiS, respectively. High-entropy oxides prepared using the hydrothermal method with an equimolar combination of five cations from six elements (Cr, Mn, Fe, Co, Ni, and Zn) can be used as a guideline for the design of high-sensitivity spinel-type composite oxide gas sensors.

Low-Dimensional Palladium on Graphite-on-Paper Substrate for Hydrogen Sensing.

To stabilize the detection signal of palladium-based hydrogen sensors on paper substrates, a graphite intermediate layer was painted on the surface of paper. The graphite-on-paper (GOP) substrate offers advantages such as good thermo-electrical conductivity, low cost, and uncomplicated preparation technology. Quasi-1-dimensional palladium (Pd) thin films with 8 nm and 60 nm thicknesses were deposited on the GOP substrates using the vacuum evaporation technique. Thanks to the unique properties of the GOP substrate, a continuous Pd microfiber network structure appeared after deposition of the ultra-thin Pd film. Additionally, the sensing performance of the palladium-based hydrogen sensor was not affected, whether using GOP or paper substrate at 25 °C. Surprisingly, heating-induced loss of sensitivity was restrained due to the increased electrical conductivity of the GOP substrate at 50 °C.

Ferromagnetism and exchange bias in compressed ilmenite-hematite solid solution as a source of planetary magnetic anomalies.

We propose a compressed ilmenite-hematite solid solution as a new potential source of Earth's magnetic anomalies. The 0.5FeTiO3·0.5Fe2O3 solid solution compressed by collision synthesis with super-high-energy ball milling showed a decrease in molar volume of approximately 1.8%. Consequently, the sample showed a saturation magnetization of 1.5 ampere square meter per kilogram (Am2/kg) at 300 kelvin, a Curie temperature of 990 kelvin, and a magnetic exchange bias below 100 kelvin, e.g., 1.7 × 105 ampere per meter at 60 kelvin. Ilmenite-hematite solid solutions are common mineral systems in most mafic igneous and metamorphic rocks, and the compressive force in the rocks is generated by the high pressure in the upper mantle or by shock events with high pressure such as the collision of these rocks with meteorites. Therefore, we consider that the compressed ilmenite-hematite solid solution is an additional candidate source of other planetary magnetic anomalies including those in the Moon and Earth.

Direct observation of potential phase at joining interface between p-MgO and n-MgFe2O4.

Visualization of the depletion layer is a significant a guideline for the material design of gas sensors. We attempted to measure the potential barrier at the interface of core-shell microspheres composed of p-MgO/n-MgFe2O4/Fe2O3 from the inside out by means of Kelvin probe force microscopy (KPFM) as a first step to visualizing enlargement of the depletion layer. As determined by high-angle annular dark-field scanning transmission electron microscopy, ca. 70% of the microspheres were hollow with a wall thickness of ca. 200 nm. Elemental mapping revealed that the hollow particles were composed of ca. 20 nm of MgO, ca. 80 nm of MgFe2O4, and ca. 100 nm of Fe2O3. A difference of 0.2 V at the p-MgO/n-MgFe2O4 interface was clarified by KPFM measurements of the hollow particles, suggesting that this difference depends on the formation of a p-n junction. The potential barrier enlarged by the formation of a p-n junction was considered to increase the resistance in air (Ra), since the Ra of the core-shell hollow microspheres was higher than that of MgO, Fe2O3, MgO-Fe2O3, and MgO/MgFe2O4/Fe2O3 particles with irregular shapes. Measurement of the potential barrier height by KPFM is a promising potential approach to tuning the gas sensitivity of oxide semiconductors.

Emergence of ferromagnetism due to charge transfer in compressed ilmenite powder using super-high-energy ball milling.

Ilmenite, FeTiO3, is a common mineral in nature, existing as an accessory phase in the most basic igneous and metamorphic rocks, for example, it is derived from the upper mantle. Therefore, an understanding of the high-pressure physics of FeTiO3 is of fundamental importance in the study of rock magnetization. Here, we provide experimental evidence of lattice compression of FeTiO3 powder using super-high-energy ball milling, enabling the very high collision energy of 420 times gravitational acceleration. A sample obtained as an ilmenite- hematite 0.5FeTiO3·0.5Fe2O3 solid solution showed a decrease in molar volume of approximately 1.8%. Consequently, the oxidation state in FeTiO3 powder was changed into almost Fe3+Ti3+, corresponding to 87% Fe3+ of the total Fe for FeTiO3, resulting in the emergence of ferromagnetism. This new ferromagnetic behaviour is of crucial importance in the study of rock magnetization which is used to interpret historical fluctuations in geomagnetism. In addition, the super-high-energy ball mill can be used to control a range of charge and spin states in transition metal oxides with high pressure.

Selective synthesis of zeolites A and X from two industrial wastes: Crushed stone powder and aluminum ash.

Crushed stone powder and aluminum ash are industrial wastes, and effective utilization of these wastes has been highly expected. Since the main components of the two wastes are Si, Al and O, those wastes can be used as starting materials for synthesis of zeolites of which some types have been commercialized as catalysts and ion-exchangers. In this study, zeolites A and X well-known as practical materials were successfully synthesized with high purity using the two industrial wastes by a mild process based on two hydrothermal treatments with intermediate acid treatment. In the first hydrothermal treatment at 150 °C, quartz in the crushed stone powder was dissolved and acid-soluble hydroxysodalite (Na8(AlSiO4)6(H2O)2(OH)2) with Si/Al = 1 and sodium aluminosilicate (Na6(AlSiO4)6) were formed. Those compounds were dissolved with HCl aq. solution. The zeolites were successfully synthesized from the second hydrothermal treatment of the yellow dried filtrates at 80 °C in NaOH aq. solution. In the process proposed, removal of Ca from the crushed stone powder was effective to formation of zeolites A and/or X. Selective synthesis of zeolites A and X was achieved by controlling the acid treatment conditions. Furthermore, the effect of the drying condition of the filtrate obtained after the acid treatment was also investigated on the differences in the product phase.

Self-Assemblies of Zinc Bacteriochlorophyll-d Analogues Having Amide, Ester, and Urea Groups as Substituents at 17-Position and Observation of Lamellar Supramolecular Nanostructures.

Chlorosomes are unique light-harvesting apparatuses in photosynthetic green bacteria. Single chlorosomes contain a large number of bacteriochlorophyll (BChl)-c, -d, -e, and -f molecules, which self-assemble without protein assistance. These BChl self-assemblies involving specific intermolecular interactions (Mg⋅⋅⋅O32 -H⋅⋅⋅O=C131 and π-π stacks of chlorin skeletons) in a chlorosome have been reported to be round-shaped rods (or tubes) with diameters of 5 or 10 nm, or lamellae with a layer spacing of approximately 2 nm. Herein, the self-assembly of synthetic zinc BChl-d analogues having ester, amide, and urea groups in the 17-substituent is reported. Spectroscopic analyses indicate that the zinc BChl-d analogues self-assemble in a nonpolar organic solvent in a similar manner to natural chlorosomal BChls with additional assistance by hydrogen-bonding of secondary amide (or urea) groups (CON-H⋅⋅⋅O=CNH). Microscopic analyses of the supramolecules of a zinc BChl-d analogue bearing amide and urea groups show round- or square-shaped rods with widths of about 65 nm. Cryogenic TEM shows a lamellar arrangement of the zinc chlorin with a layer spacing of 1.5 nm inside the rod. Similar thick rods are also visible in the micrographs of self-assemblies of zinc BChl-d analogues with one or two secondary amide moieties in the 17-substituent.

Nanotubes of Biomimetic Supramolecules Constructed by Synthetic Metal Chlorophyll Derivatives.

Various supramolecular nanotubes have recently been built up by lipids, peptides, and other organic molecules. Major light-harvesting (LH) antenna systems in a filamentous anoxygenic phototroph, Chloroflexus (Cfl.) aurantiacus, are called chlorosomes and contain photofunctional single-wall supramolecular nanotubes with approximately 5 nm in their diameter. Chlorosomal supramolecular nanotubes of Cfl. aurantiacus are constructed by a large amount of bacteriochlorophyll(BChl)-c molecules. Such a pigment self-assembles in a chlorosome without any assistance from the peptides, which is in sharp contrast to the other natural photosynthetic LH antennas. To mimic chlorosomal supramolecular nanotubes, synthetic models were prepared by the modification of naturally occurring chlorophyll(Chl)-a molecule. Metal complexes (magnesium, zinc, and cadmium) of the Chl derivative were synthesized as models of natural chlorosomal BChls. These metal Chl derivatives self-assembled in hydrophobic environments, and their supramolecules were analyzed by spectroscopic and microscopic techniques. Cryo-transmission electron microscopic images showed that the zinc and cadmium Chl derivatives could form single-wall supramolecular nanotubes and their outer and inner diameters were approximately 5 and 3 nm, respectively. Atomic force microscopic images suggested that the magnesium Chl derivative formed similar nanotubes to those of the corresponding zinc and cadmium complexes. Three chlorosomal single-wall supramolecular nanotubes of the metal Chl derivatives were prepared in the solid state and would be useful as photofunctional materials.

Electric-field-induced viscosity change of a nematic liquid crystal with gold nanoparticles.

The electro-rheological (ER) effect of a composite material consisting of a nematic liquid crystal (LC) and gold nanoparticles covered with mesogenic groups is discussed. The gold nanoparticles are covered by alkyl chains and liquid-crystalline compounds. The influences of the alkyl-chain length and the coverage by the alkyl chain and the mesogenic group on the miscibility of the nanoparticles with the LC are investigated by polarizing optical microscopy (POM). The presence of the gold nanoparticles in the nematic LC (5CB) leads to an enhanced ER response compared to that observed for 5CB. The prominent ER effect observed in this study is supported by the two mechanisms proposed, that is, the homogeneous and heterogeneous mechanisms. This study demonstrates the potential of a hybrid system consisting of an LC and gold nanoparticles to improve the ER effect.

Quenching ilmenite with a high-temperature and high-pressure phase using super-high-energy ball milling.

The mass production of highly dense oxides with high-temperature and high-pressure phases allows us to discover functional properties that have never been developed. To date, the quenching of highly dense materials at the gramme-level at ambient atmosphere has never been achieved. Here, we provide evidence of the formation of orthorhombic Fe2TiO4 from trigonal FeTiO3 as a result of the high-temperature (>1250 K) and high-pressure (>23 GPa) condition induced by the high collision energy of 150 gravity generated between steel balls. Ilmenite was steeply quenched by the surrounding atmosphere, when iron-rich ilmenite (Fe2TiO4) with a high-temperature and high-pressure phase was formed by planetary collisions and was released from the collision points between the balls. Our finding allows us to infer that such intense planetary collisions induced by high-energy ball milling contribute to the mass production of a high-temperature and high-pressure phase.

Construction of chlorosomal rod self-aggregates in the solid state on any substrates from synthetic chlorophyll derivatives possessing an oligomethylene chain at the 17-propionate residue.

Chlorosomes are one of the most unique natural light-harvesting antennas and their supramolecular nanostructures are still under debate. Chlorosomes contain bacteriochlorophyll (BChl)-c, d and e molecules and these pigments self-aggregate under a hydrophobic environment inside a chlorosome. The self-aggregates are mainly constructed by the following three interactions: hydrogen bonding, coordination bonding and π-π stacking. Supramolecular nanostructures of self-aggregated BChls have been widely investigated by spectroscopic and microscopic techniques. Model compounds of such chlorosomal BChl molecules have been synthesized and the effects of esterified long alkyl chains at the 17-propionate residue for their self-aggregation have been studied. Structurally simple zinc chlorophyll derivatives possessing an oligomethylene chain as the esterifying group at the 17-propionate residue were prepared as chlorosomal BChl models. The synthetic zinc BChls self-aggregated in nonpolar organic solvents to give precipitates. The resulting insoluble self-aggregated solids were investigated on a variety of substrates, including hydrophobic, neutral and hydrophilic substrates, by visible absorption, circular dichroism and polarized light absorption spectroscopies, as well as atomic force, transmission electron and scanning electron microscopies. The self-aggregates of synthetic Zn-BChls formed rods with an approximately 5 nm diameter and wires with further elongated growth of the rods (aspect ratio >200). The diameter size was consistent with that estimated for natural chlorosomal rods in a filamentous anoxygenic phototroph, Chloroflexus aurantiacus. The supramolecular formation and stability of the rod on the examined substrates depended on the length of an oligomethylene chain at the 17-propionate residue as well as on the surface properties. Especially, the number of the 5 nm rods on the substrates increased with an elongation of the chain.

Solvent-assisted organized structures based on amphiphilic anion-responsive pi-conjugated systems.

The synthesis of amphiphilic pi-conjugated acyclic oligopyrroles and the formation of solvent-assisted aggregates are reported. We have prepared various types of BF(2) complexes of 1,3-dipyrrolylpropane-1,3-diones bearing aryl rings substituted with hydrophilic polyethyleneglycol (PEG) chains, both as acyclic anion receptors and as building subunits for organized architectures based on pi-pi stacking. The formation of supramolecular H-type assemblies of these "amphiphilic" derivatives in aqueous solution was suggested by UV/Vis and fluorescence spectroscopy and further supported by (1)H NMR and dynamic light scattering (DLS) analyses. Cryogenic transmission electron microscopy (cryo-TEM) analyses of the aqueous solutions suggest that the fabrication of nanoscale network structures and vesicles depends on the peripheral substituents. The H-aggregates in aqueous solution are sensitive to the conditions required for transformation into monomers through replacement with miscible solvents such as alcohols and into J-type aggregates by water evaporation and freeze-drying procedures. However, they are fairly stable and sustainable to anion binding, whereas on CH(2)Cl(2) extraction they are transformed into other assembled modes but remain in the aqueous solution. The metastable states of affairs for distributions between two immiscible solvents are controlled by the orders of solution preparation; this also suggests that the formation of stable assemblies is assisted by water molecules. Furthermore, assemblies in which the stacking modes depend on the aliphatic side chains are also observed in a nonpolar hydrocarbon solvent.