Innovative inorganic synthesis

No abstract available

Revisiting the hydrogen storage behavior of the Na-O-H system

Solid-state reactions between sodium hydride and sodium hydroxide are unusual among hydride-hydroxide systems since hydrogen can be stored reversibly. In order to understand the relationship between hydrogen uptake/release properties and phase/structure evolution, the dehydrogenation and hydrogenation behavior of the Na-O-H system has been investigated in detail both ex- and in-situ. Simultaneous thermogravimetric-differential thermal analysis coupled to mass spectrometry (TG-DTA-MS) experiments of NaH-NaOH composites reveal two principal features: Firstly, an H2 desorption event occurring between 240 and 380 °C and secondly an additional endothermic process at around 170 °C with no associated weight change. In-situ high-resolution synchrotron powder X-ray diffraction showed that NaOH appears to form a solid solution with NaH yielding a new cubic complex hydride phase below 200 °C. The Na-H-OH phase persists up to the maximum temperature of the in-situ diffraction experiment shortly before dehydrogenation occurs. The present work suggests that not only is the inter-phase synergic interaction of protic hydrogen (in NaOH) and hydridic hydrogen (in NaH) important in the dehydrogenation mechanism, but that also an intra-phase Hδ+… Hδ– interaction may be a crucial step in the desorption process

Unusual structural phenomena in the reaction of copper and nickel dihalides with NH_3(g) at ambient conditions

No abstract available

Recent progress in the synthesis of nanostructured magnesium hydroxide

This review highlights synthetic routes for producing nanostructured magnesium hydroxide and focuses on how these various preparative approaches can produce Mg(OH)2 nanoparticles with controlled size and morphology. Mg(OH)2 nanocrystals with rod-, needle-, hollow tube- or platelet-like morphology can be synthesised by the modification of chemical and physical experimental parameters such as the selection of magnesium precursor, solvent and temperature or by employing surface modifiers and templates. Techniques based on hydrothermal/solvothermal treatments, microwave heating and (co-)precipitation are dominant in the production of Mg(OH)2 at the nanoscale, but other materials design approaches are now emerging. Bulk Mg(OH)2 has been extensively studied over decades and finds use in a wide range of applications. Moreover, the hydroxide can also serve as a precursor for other commercially important materials such as MgO. Nanostructuring the material has proven extremely useful in modifying some of its most important properties – not least enhancing the performance of Mg(OH)2 as a non-toxic flame retardant – but equally it is creating new avenues of applied research. We evaluate herein the latest efforts to design novel synthesis routes to nano-Mg(OH)2, to understand the mechanisms of crystallite growth and to tailor microstructure towards specific properties and applications

Ammonia uptake and release in the MnX₂–NH₃ (X = Cl, Br) systems and structure of the Mn(NH₃)nX₂ (n = 6, 2) ammines

Hexa-ammine complexes, Mn(NH<sub>3</sub>)<sub>6</sub>X<sub>2</sub> (X = Cl, Br), have been synthesized by ammoniation of the corresponding transition metal halide and characterized by Powder X-ray diffraction (PXRD) and Raman spectroscopy. The hexa-ammine complexes are isostructural (Cubic,Fm-3m, Z = 4; a = 10.2742(6) Å and 10.527(1) Å for X = Cl, Br respectively). Temperature programmed desorption (TPD) demonstrated that ammonia release from Mn(NH<sub>3</sub>)<sub>6</sub>X<sub>2</sub> complexes occurred in three stages corresponding to the release of 4, 1 and 1 NH<sub>3</sub> equivalents respectively. The chloride and bromide both exhibit a deammoniation onset temperature below 323 K. The di-ammoniates from the first desorption step were isolated during TPD measurements and their crystal structures determined by Rietveld refinement against PXRD data (X = Cl: orthorhombicCmmm, a = 8.1991(9) Å, b = 8.2498(7) Å, c = 3.8212(4) Å, Z = 2; X = Br: orthorhombic Pbam, a = 6.0109(5) Å, b = 12.022(1) Å, c = 4.0230(2) Å, Z= 2)

Ni(NH3)2(NO3)2 – A 3-D network through bridging nitrate units isolated from the thermal decomposition of nickel hexammine dinitrate

Nickel nitrate diammine, Ni(NH3)2(NO3)2, can be synthesised from the thermal decomposition of nickel nitrate hexammine, Ni[(NH3)6](NO3)2. The hexammine decomposes in two distinct major stages; the first releases 4 equivalents of ammonia while the second involves the release of NOx, N2, and H2O to yield NiO. The intermediate diammine compound can be isolated following the first deammoniation step or synthesised as a single phase from the hexammine under vacuum. Powder X-ray diffraction (PXD) experiments have allowed the structure of Ni(NH3)2(NO3)2 to be solved for the first time. The compound crystallises in orthorhombic space group Pca21 (a = 11.0628 (5) Å, b = 6.0454 (3) Å, c = 9.3526 (4) Å; Z = 4) and contains 11 non-hydrogen atoms in the asymmetric unit. Fourier transform infrared (FTIR) spectroscopy demonstrates that the bonding in the ammine is consistent with the structure determined by PXD

Ni(NH3)2(NO3)2 – A 3-D network through bridging nitrate units isolated from the thermal decomposition of nickel hexammine dinitrate

Nickel nitrate diammine, Ni(NH3)2(NO3)2, can be synthesised from the thermal decomposition of nickel nitrate hexammine, Ni[(NH3)6](NO3)2. The hexammine decomposes in two distinct major stages; the first releases 4 equivalents of ammonia while the second involves the release of NOx, N2, and H2O to yield NiO. The intermediate diammine compound can be isolated following the first deammoniation step or synthesised as a single phase from the hexammine under vacuum. Powder X-ray diffraction (PXD) experiments have allowed the structure of Ni(NH3)2(NO3)2 to be solved for the first time. The compound crystallises in orthorhombic space group Pca21 (a = 11.0628 (5) Å, b = 6.0454 (3) Å, c = 9.3526 (4) Å; Z = 4) and contains 11 non-hydrogen atoms in the asymmetric unit. Fourier transform infrared (FTIR) spectroscopy demonstrates that the bonding in the ammine is consistent with the structure determined by PXD

Rapid surfactant-free synthesis of Mg(OH)2 nanoplates and pseudomorphic dehydration to MgO

Magnesium hydroxide nanoplates ca. 50 nm in thickness can be prepared over minute timescales via hydrothermal synthesis in a multimode cavity (MMC) microwave reactor. This approach allows ca. 1 g of single-phase Mg(OH)2 to be synthesised in under 3 minutes without the requirement of surfactants or non-aqueous solvents. The hydroxide nanomaterial dehydrates at temperatures >200 K below that of the equivalent bulk material and can be utilised as a precursor for the pseudomorphic synthesis of nanoplates of MgO as investigated by TG-DTA-MS, XRD and SEM measurements. Equally, the pseudomorphic synthesis can be performed by irradiating the Mg(OH)2 nanomaterial with microwaves for 6 minutes to produce single phase MgO

Microwave-assisted synthesis of ZnO-rGO core-shell nanorod hybrids with photo- and electro-catalytic activity

The unique two‐dimensional structure and surface chemistry of reduced graphene oxide (rGO) along with its high electrical conductivity can be exploited to modify the electrochemical properties of ZnO nanoparticles (NPs). ZnO‐rGO nanohybrids can be engineered in a simple new two‐step synthesis, which is both fast and energy‐efficient. The resulting hybrid materials show excellent electrocatalytic and photocatalytic activity. The structure and composition of the as‐prepared bare ZnO nanorods (NRs) and the ZnO‐rGO hybrids have been extensively characterised and the optical properties subsequently studied by UV‐Vis spectroscopy and photoluminescence (PL) spectroscopy (including decay life time measurements). The photocatalytic degradation of Rhodamine B (RhB) dye is enhanced using the ZnO‐rGO hybrids as compared to bare ZnO NRs. Further, potentiometry comparing ZnO and ZnO‐rGO electrodes reveals a featureless capacitive background for an Ar‐saturated solution whereas for an O 2 ‐saturated solution a well‐defined redox peak was observed using both electrodes. The change in reduction potential and significant increase in current density demonstrates that the hybrid core‐shell NRs possess remarkable electrocatalytic activity for the oxygen reduction reaction (ORR) as compared to NRs of ZnO alone

van der Waals contact engineering of graphene field-effect transistors for large-area flexible electronics

Graphene has great potential for high-performance flexible electronics. Although studied for more than a decade, contacting graphene efficiently, especially for large-area, flexible electronics, is still a challenge. Here, by engineering the graphene-metal van der Waals (vdW) contact, we demonstrate that ultra-low contact resistance is achievable via a bottom-contact strategy incorporating a simple transfer process without any harsh thermal treatment (>150°C). The majority of the fabricated devices show contact resistances below 200 Ω·µm with values as low as 65 Ω·µm achievable. This is on a par with the state-of-the-art top- and edge-contacted graphene field-effect transistors (GFETs). Further, our study reveals that these contacts, despite the presumed weak nature of the vdW interaction, are stable under various bending conditions, thus guaranteeing compatibility with flexible electronics with improved performance. This work illustrates the potential of the previously underestimated vdW contact approach for large-area flexible electronics