Reversible Hydrogen Uptake/Release over a Sodium Phenoxide–Cyclohexanolate Pair

Hydrogen uptake and release in arene–cycloalkane pairs provide an attractive opportunity for on‐board and off‐board hydrogen storage. However, the efficiency of arene–cycloalkane pairs currently is limited by unfavorable thermodynamics for hydrogen release. It is shown here that the thermodynamics can be optimized by replacement of H in the ‐OH group of cyclohexanol and phenol with alkali or alkaline earth metals. The enthalpy change upon dehydrogenation decreases substantially, which correlates with the delocalization of the oxygen electron to the benzene ring in phenoxides. Theoretical calculations reveal that replacement of H with a metal leads to a reduction of the HOMO–LUMO energy gap and elongation of the C?H bond in the α site in cyclohexanolate, which indicates that the cyclohexanol is activated upon metal substitution. The experimental results demonstrate that sodium phenoxide–cyclohexanolate, an air‐ and water‐stable pair, can desorb hydrogen at ca. 413 K and 373 K in the solid form and in an aqueous solution, respectively. Hydrogenation, on the other hand, is accomplished at temperatures as low as 303 K.     

Molecular structure and dynamics in the low temperature (orthorhombic) phase of NH3BH3

Variable temperature 2H NMR experiments on the orthorhombic phase of selectively deuterated NH3BH3 spanning the static to fast exchange limits of the borane and amine motions are reported. New values of the electric field gradient (EFG) tensor parameters have been obtained from the static 2H spectra of V(zz) = 1.652 (+/-0.082) x 10(21) V/m(2) and eta = 0.00 +/- 0.05 for the borane hydrogens and V(zz) = 2.883 (+/-0.144) x 10(21) V/m(2) and eta = 0.00 +/- 0.05 for the amine hydrogens. The molecular symmetry inferred from the observation of equal EFG tensors for the three borane hydrogens and likewise for the three amine hydrogens is in sharp contrast with the C(s) symmetry derived from diffraction studies. The origin of the apparent discrepancy has been investigated using molecular dynamics methods in combination with electronic structure calculations of NMR parameters, bond lengths, and bond angles. The computation of parameters from a statistical ensemble rather than from a single set of atomic Cartesian coordinates gives values that are in close quantitative agreement with the 2H NMR electric field gradient tensor measurements and are more consistent with the molecular symmetry revealed by the NMR spectra.     

Effect of manganese stress on the mineral content of the leaves of wheat seedlings by use of X-ray fluorescence excited by synchrotron radiation

The present study describes the potential of the synchrotron radiation based X-ray fluorescence spectroscopy technique for the rapid, sensitive, user friendly and simultaneous monitoring of the changes in the elemental profile of the wheat seedlings stressed by excess manganese (Mn). For this, X-ray fluorescence spectra of the leaves of the control and Mn treated wheat seedlings have been recorded by synchrotron radiation X-ray of energy 15?keV. The analyses of the recorded spectra show the presence of elements chlorine, potassium, calcium, manganese, iron, copper, nickel, and zinc. A calibration-free approach, PyMca has been used for the quantitative estimation of the detected elements in the leaves of the control and Mn treated wheat seedlings. The excess supply of Mn to wheat seedlings results in the accumulation of manganese in the leaves of the seedlings. The accumulation of manganese in wheat seedlings negatively affects the uptake and translocation of calcium, potassium, and iron while it has stimulating effect on the uptake of copper and zinc.     

Mixed-ligand metal complexes containing an ONS Schiff base and imidazole/benzimidazole ligands: synthesis,characterization, crystallography and biological activity

Salicylaldehyde-4-methylthiosemicarbazone (H₂MTSali) has been prepared via the condensation reaction of 4-methyl-3-thiosemicarbazide and salicylaldehyde. Four new mixed-ligand copper(II) and nickel(II) complexes with a general formula [M(MTSali)L] (M = Cu²⁺ or Ni²⁺; L = co-ligand) were synthesized, where L is either imidazole (im) or benzimidazole (bzim). The Schiff base and its mixed-ligand complexes were characterized by IR and UV/Vis spectroscopy, and the complexes by molar conductivity and magnetic susceptibility measurements. The spectroscopic data indicated that the Schiff base behaves as a tridentate ONS donor ligand coordinating via the phenoxide-oxygen, azomethine-nitrogen, and thiolate-sulphur atoms. Magnetic data indicate a square planar environment for the nickel(II) complexes while molar conductance values indicate that the metal complexes are essentially non-electrolytes in DMSO solution. X-ray crystallography shows Cu(MTSali)bzim (1) and Ni(MTSali)bzim (3) to be isostructural, with the metal(II) ions being coordinated by a N₂OS donor set that defines an approximate square planar geometry; in both cases, the benzimidazole is splayed with respect to the coordination plane. The copper(II) complexes were active against MDA-MB-231 and MCF-7 breast cancer cell lines, more so than H₂MTSali, whereas the nickel(II) complexes were inactive.     

Recovery of iron/iron oxide nanoparticles from solution: comparison of methods and their effects

Most methods currently being used to recover Fe⁰-core/oxide-shell nanoparticles from solutions (including the solvents they are synthesized or stored in) are potentially problematic because they may alter the particle composition (e.g., depositing salts formed from solutes) or leave the particles prone to transformations during subsequent storage and handling (e.g., due to residual moisture). In this study, several methods for recovery of nanoparticles from aqueous solution were studied to determine how they affect the structure and reactivity of the recovered materials. Simple washing of the nanoparticles during vacuum filtration (i.e., “flash drying”) can leave up to ~17 wt% residual moisture. Modeling calculations suggest this moisture is mostly capillary or matric water held between particles and particle aggregates, which can be removed by drying for short periods at relative vapor pressures below 0.9. Flash drying followed by vacuum drying, all under N₂, leaves no detectable residue from precipitation of solutes (detectable by X-ray photoelectron spectroscopy, XPS), no significant changes in overall particle composition or structure (determined by transmission electron microscopy, TEM), and negligible residual moisture (by thermogravimetric analysis, TGA). While this improved flash-drying protocol may be the preferred method for recovering nanoparticles for many purposes, we found that Fe⁰-core/oxide-shell nanoparticles still exhibit gradual aging during storage when characterized electrochemically with voltammetry.     

Reversible dehydrogenation of magnesium borohydride to magnesium triborane in the solid state under moderate conditions

Thermal decomposition of magnesium borohydride, Mg(BH(4))(2), in the solid state was studied by a combination of PCT, TGA/MS and NMR spectroscopy. Dehydrogenation of Mg(BH(4))(2) at 200 °C en vacuo results in the highly selective formation of magnesium triborane, Mg(B(3)H(8))(2). This process is reversible at 250 °C under 120 atm H(2). Dehydrogenation at higher temperature, >300 °C under a constant argon flow of 1 atm, produces a complex mixture of polyborane species. A borohydride condensation mechanism involving metal hydride formation is proposed.     

Immobilizing Highly Catalytically Active Pt Nanoparticles inside the Pores of Metal-Organic Framework: A Double Solvents Approach

Ultrafine Pt nanoparticles were successfully immobilized inside the pores of a metal-organic framework, MIL-101, without aggregation of Pt nanoparticles on the external surfaces of framework by using a "double solvents" method. TEM and electron tomographic measurements clearly demonstrated the uniform three-dimensional distribution of the ultrafine Pt NPs throughout the interior cavities of MIL-101. The resulting Pt@MIL-101 composites represent the first highly active MOF-immobilized metal nanocatalysts for catalytic reactions in all three phases: liquid-phase ammonia borane hydrolysis, solid-phase ammonia borane thermal dehydrogenation, and gas-phase CO oxidation.     

Chemical routes to nanocrystalline thermoelectrically relevant AgPb(m)SbTe(m+2) materials

A direct synthesis of nanoparticles of the thermoelectrically relevant AgPbmSbTem+2 materials (m = 0, 1, 2) was accomplished in reverse micelles. The procedure offers several distinct advantages and opens the field for experimentation of thermoelectric properties for nanoparticle-derived materials.     

Electrochemically Tunable Proton‐Coupled Electron Transfer in Pd‐Catalyzed Benzaldehyde Hydrogenation

Acid functionalization of a carbon support allows to enhance the electrocatalytic activity of Pd to hydrogenate benzaldehyde to benzyl alcohol proportional to the concentration of Brønsted‐acid sites. In contrast, the hydrogenation rate is not affected when H₂ is used as a reduction equivalent. The different responses to the catalyst properties are shown to be caused by differences in the hydrogenation mechanism between the electrochemical and the H₂‐induced hydrogenation pathways. The enhancement of electrocatalytic reduction is realized by the participation of support‐generated hydronium ions in the proximity of the metal particles.