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Inorganics
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  This is an Open Access Journal Open Access journal
     ISSN (Online) 2304-6740
     Published by MDPI Homepage  [124 journals]
  • Inorganics, Vol. 2, Pages 155-167: Electromechanical Properties of Small
           Transition-Metal Dichalcogenide Nanotubes

    • Authors: Nourdine Zibouche, Mahdi Ghorbani-Asl, Thomas Heine, Agnieszka Kuc
      Pages: 155 - 167
      Abstract: Transition-metal dichalcogenide nanotubes (TMC-NTs) are investigated for their electromechanical properties under applied tensile strain using density functional-based methods. For small elongations, linear strain-stress relations according to Hooke’s law have been obtained, while for larger strains, plastic behavior is observed. Similar to their 2D counterparts, TMC-NTs show nearly a linear change of band gaps with applied strain. This change is, however, nearly diameter-independent in case of armchair forms. The semiconductor-metal transition occurs for much larger deformations compared to the layered tube equivalents. This transition is faster for heavier chalcogen elements, due to their smaller intrinsic band gaps. Unlike in the 2D forms, the top of valence and the bottom of conduction bands stay unchanged with strain, and the zigzag NTs are direct band gap materials until the semiconductor-metal transition. Meanwhile, the applied strain causes modification in band curvature, affecting the effective masses of electrons and holes. The quantum conductance of TMC-NTs starts to occur close to the Fermi level when tensile strain is applied.
      PubDate: 2014-04-23
      DOI: 10.3390/inorganics2020155
      Issue No: Vol. 2, No. 2 (2014)
       
  • Inorganics, Vol. 2, Pages 168-176: Qualifying the Role of Indium in the
           Multiple-Filled Ce0.1InxYb0.2Co4Sb12 Skutterudite

    • Authors: Jennifer Graff, Jian He, Terry Tritt
      Pages: 168 - 176
      Abstract: Literature confirms an improvement in the overall TE properties due to the in situ InSb nano-dispersed phases located along the grain boundaries in several double-filled InxYzCo4Sb12 skutterudites. However, the single-filled InxCo4Sb12 reports contribute enhancement in TE properties solely on the nature of In as a void filler. To qualify the effect of In on the TE properties on multiple-filled skutterudites several multiple-filled Ce0.1InxYb0.2Co4Sb12 skutterudite samples, with nominal composition Ce0.1InyYb0.2Co4Sb12 (0 ≤ y ≤ 0.2), were synthesized. A double-filled base-line sample Ce0.1Yb0.2Co4Sb12 was also synthesized and characterized to create a much fuller depiction of the nature of In and its impact on the TE properties of the filled Co4Sb12-based skutterudite materials. Our results confirm that small amounts of In can be effective at increasing electrical conductivity in the multiple-filled Ce0.1InyYb0.2Co4Sb12 skutterudite. An increased mobility and thus electrical conductivity result in a 15% increase in the dimensionless Figure of Merit, ZT, in the nominal sample composition, Ce0.1In0.05Yb0.2Co4Sb12, which exhibits a state of the art ZT > 1.4 at T = 820 K.
      PubDate: 2014-04-29
      DOI: 10.3390/inorganics2020168
      Issue No: Vol. 2, No. 2 (2014)
       
  • Inorganics, Vol. 2, Pages 177-190: Single- to Triple-Wall WS2 Nanotubes
           Obtained by High-Power Plasma Ablation of WS2 Multiwall Nanotubes

    • Authors: Volker Brüser, Ronit Popovitz-Biro, Ana Albu-Yaron, Tommy Lorenz, Gotthard Seifert, Reshef Tenne, Alla Zak
      Pages: 177 - 190
      Abstract: The synthesis of inorganic nanotubes (INT) from layered compounds of a small size (<10 nm in diameter) and number of layers (<4) is not a trivial task. Calculations based on density functional tight-binding theory (DFTB) predict that under highly exergonic conditions, the reaction could be driven into a “window” of (meta-) stability, where 1–3-layer nanotubes will be formed. Indeed, in this study, single- to triple-wall WS2 nanotubes with a diameter of 3–7 nm and a length of 20–100 nm were produced by high-power plasma irradiation of multiwall WS2 nanotubes. As target materials, plane crystals (2H), quasi spherical nanoparticles (IF) and multiwall, 20–30 layers, WS2 nanotubes were assessed. Surprisingly, only INT-WS2 treated by plasma resulted in very small, and of a few layers, “daughter” nanotubules. The daughter nanotubes occur mostly attached to the outer surface of the predecessor, i.e., the multiwall “mother” nanotubes. They appear having either a common growth axis with the multiwall nanotube or tilted by approximately 30° or 60° with respect to its axis. This suggests that the daughter nanotubes are generated by exfoliation along specific crystallographic directions. A growth mechanism for the daughter nanotubes is proposed. High resolution transmission and scanning electron microscopy (HRTEM/HRSEM) analyses revealed the distinctive nanoscale structures and helped elucidating their growth mechanism.
      PubDate: 2014-04-29
      DOI: 10.3390/inorganics2020177
      Issue No: Vol. 2, No. 2 (2014)
       
  • Inorganics, Vol. 2, Pages 1-15: Bottom-Up, Wet Chemical Technique for the
           Continuous Synthesis of Inorganic Nanoparticles

    • Authors: Annika Betke, Guido Kickelbick
      Pages: 1 - 15
      Abstract: Continuous wet chemical approaches for the production of inorganic nanoparticles are important for large scale production of nanoparticles. Here we describe a bottom-up, wet chemical method applying a microjet reactor. This technique allows the separation between nucleation and growth in a continuous reactor environment. Zinc oxide (ZnO), magnetite (Fe3O4), as well as brushite (CaHPO4·2H2O), particles with a small particle size distribution can be obtained continuously by using the rapid mixing of two precursor solutions and the fast removal of the nuclei from the reaction environment. The final particles were characterized by FT-IR, TGA, DLS, XRD and SEM techniques. Systematic studies on the influence of the different process parameters, such as flow rate and process temperature, show that the particle size can be influenced. Zinc oxide was obtained with particle sizes between 44 nm and 102 nm. The obtained magnetite particles have particle sizes in the range of 46 nm to 132 nm. Brushite behaves differently; the obtained particles were shaped like small plates with edge lengths between 100 nm and 500 nm.
      PubDate: 2014-01-27
      DOI: 10.3390/inorganics2010001
      Issue No: Vol. 2, No. 1 (2014)
       
  • Inorganics, Vol. 2, Pages 16-28: Investigation into the Incorporation of
           Phosphate into BaCe1−yAyO3−y/2 (A = Y, Yb, In)

    • Authors: Alaric Smith, Peter Slater
      Pages: 16 - 28
      Abstract: In this paper we examine the effect of doping phosphate into BaCe1−yAyO3−y/2 (A = Y, Yb, In). The samples were analysed through a combination of X-ray diffraction, TGA, Raman spectroscopy and conductivity measurements. The results showed that phosphate could be incorporated into this system up to the 10% doping level, although this required an increased Y/Yb/In content, e.g., BaCe0.6(Y/In/Yb)0.3P0.1O2.9. The phosphate doping was, however, shown to lead to a decrease in conductivity; although at low phosphate levels high conductivities were still observed, e.g., for BaCe0.65Y0.3P0.05O2.875, σ = 4.3 × 10−3 S cm−1 at 600 °C in wet N2. In terms of the effect of phosphate incorporation on the CO2 stability, it was shown to lead to a small improvement for the In containing samples, whereas the yttrium doped compositions showed no change in CO2 stability.
      PubDate: 2014-01-29
      DOI: 10.3390/inorganics2010016
      Issue No: Vol. 2, No. 1 (2014)
       
  • Inorganics, Vol. 2, Pages 29-78: Chemistry of Ammonothermal Synthesis

    • Authors: Theresia Richter, Rainer Niewa
      Pages: 29 - 78
      Abstract: Ammonothermal synthesis is a method for synthesis and crystal growth suitable for a large range of chemically different materials, such as nitrides (e.g., GaN, AlN), amides (e.g., LiNH2, Zn(NH2)2), imides (e.g., Th(NH)2), ammoniates (e.g., Ga(NH3)3F3, [Al(NH3)6]I3 · NH3) and non-nitrogen compounds like hydroxides, hydrogen sulfides and polychalcogenides (e.g., NaOH, LiHS, CaS, Cs2Te5). In particular, large scale production of high quality crystals is possible, due to comparatively simple scalability of the experimental set-up. The ammonothermal method is defined as employing a heterogeneous reaction in ammonia as one homogenous fluid close to or in supercritical state. Three types of milieus may be applied during ammonothermal synthesis: ammonobasic, ammononeutral or ammonoacidic, evoked by the used starting materials and mineralizers, strongly influencing the obtained products. There is little known about the dissolution and materials transport processes or the deposition mechanisms during ammonothermal crystal growth. However, the initial results indicate the possible nature of different intermediate species present in the respective milieus.
      PubDate: 2014-02-28
      DOI: 10.3390/inorganics2010029
      Issue No: Vol. 2, No. 1 (2014)
       
  • Inorganics, Vol. 2, Pages 79-95: New Type-I and Type-II Clathrates in the
           Systems Cs–Na–Ga–Si, Rb–Na–Ga–Si, and
           Rb–Na–Zn–Si

    • Authors: Marion Schäfer, Svilen Bobev
      Pages: 79 - 95
      Abstract: Systematic studies in the systems Cs–Na–Ga–Si, Rb–Na–Ga–Si, and Rb–Na–Zn–Si yielded the novel type-I clathrates with refined compositions Cs6Na2Ga8.25Si37.75(3), Rb6.34Na1.66(2)Ga8.02Si37.98(3), and Rb5.20Na2.80(4)Zn3.85Si42.15(2) (cubic, ), as well as the type-II clathrates with formulae Cs8Na16Ga22.7Si113.3(1), Rb8.4Na15.6(1)Ga19.6Si116.4(1), and Rb8Na16Zn8.4Si127.6(1) (cubic, ). In each system, the type-I and -II compounds are always co-crystallizing, irrespective of the reaction conditions. The structures derived from single-crystal X-ray diffraction confirm complete ordering of Cs and Na atoms, and nearly complete ordering of the Rb and Na guest atoms. The framework-building Si atoms are randomly substituted by Ga or Zn atoms on all framework sites with notable difference in the substitution patterns between the type-I and type-II structure. This, and other details of the crystal chemistry are discussed in this paper.
      PubDate: 2014-03-18
      DOI: 10.3390/inorganics2010079
      Issue No: Vol. 2, No. 1 (2014)
       
  • Inorganics, Vol. 2, Pages 96-114: Syntheses of Macromolecular Ruthenium
           Compounds: A New Approach for the Search of Anticancer Drugs

    • Authors: Andreia Valente, M. Garcia
      Pages: 96 - 114
      Abstract: The continuous rising of the cancer patient death rate undoubtedly shows the pressure to find more potent and efficient drugs than those in clinical use. These agents only treat a narrow range of cancer conditions with limited success and are associated with serious side effects caused by the lack of selectivity. In this frame, innovative syntheses approaches can decisively contribute to the success of “smart compounds” that might be only selective and/or active towards the cancer cells, sparing the healthy ones. In this scope, ruthenium chemistry is a rising field for the search of proficient metallodrugs by the use of macromolecular ruthenium complexes (dendrimers and dendronized polymers, coordination-cage and protein conjugates, nanoparticles and polymer-“ruthenium-cyclopentadienyl” conjugates) that can take advantage of the singularities of tumor cells (vs. healthy cells).
      PubDate: 2014-03-21
      DOI: 10.3390/inorganics2010096
      Issue No: Vol. 2, No. 1 (2014)
       
  • Inorganics, Vol. 2, Pages 115-131: Diarylplatinum(II) Compounds as
           Versatile Metallating Agents in the Synthesis of Cyclometallated Platinum
           Compounds with N-Donor Ligands

    • Authors: Margarita Crespo
      Pages: 115 - 131
      Abstract: This review deals with the reactions of diarylplatinum(II) complexes with N-donor ligands to produce a variety of cycloplatinated compounds including endo-five-, endo-seven-, endo-six- or exo-five-membered platinacycles. The observed reactions result from a series of oxidative addition/reductive elimination processes taking place at platinum(II)/platinum(IV) species and involving C–X (X = H, Cl, Br) bond activation, arene elimination, and, in some cases, Caryl–Caryl bond formation.
      PubDate: 2014-03-21
      DOI: 10.3390/inorganics2010115
      Issue No: Vol. 2, No. 1 (2014)
       
  • Inorganics, Vol. 2, Pages 132-154: Comparative Issues of Cathode Materials
           for Li-Ion Batteries

    • Authors: Christian Julien, Alain Mauger, Karim Zaghib, Henri Groult
      Pages: 132 - 154
      Abstract: After an introduction to lithium insertion compounds and the principles of Li-ion cells, we present a comparative study of the physical and electrochemical properties of positive electrodes used in lithium-ion batteries (LIBs). Electrode materials include three different classes of lattices according to the dimensionality of the Li+ ion motion in them: olivine, layered transition-metal oxides and spinel frameworks. Their advantages and disadvantages are compared with emphasis on synthesis difficulties, electrochemical stability, faradaic performance and security issues.
      PubDate: 2014-03-25
      DOI: 10.3390/inorganics2010132
      Issue No: Vol. 2, No. 1 (2014)
       
  • Inorganics, Vol. 1, Pages 1-2: Welcome to Inorganics: A New Open Access,
           Inclusive Forum for Inorganic Chemistry

    • Authors: Duncan Gregory
      Pages: 1 - 2
      Abstract: One of the beauties of inorganic chemistry is its sheer diversity. Just as chemistry sits at the centre of the sciences, inorganic chemistry sits at the centre of chemistry itself. Inorganic chemists are fortunate in having the entire periodic table at their disposal, providing a palette for the creation of a multitude of rich and diverse compounds and materials from the simplest salts to the most complex of molecular species. It follows that the language of inorganic chemistry can thus be a demanding one, accommodating sub-disciplines with very different perspectives and frames of reference. One could argue that it is the unequivocal breadth of inorganic chemistry that empowers inorganic chemists to work at the interfaces, not just between the traditional Inorganic-Organic-Physical boundaries of the discipline, but in the regions where chemistry borders the other physical and life sciences, engineering and socio-economics.
      PubDate: 2013-06-17
      DOI: 10.3390/inorganics1010001
      Issue No: Vol. 1, No. 1 (2013)
       
  • Inorganics, Vol. 1, Pages 3-13: I62− Anion Composed of Two
           Asymmetric Triiodide Moieties: A Competition between Halogen and Hydrogen
           Bond

    • Authors: Martin van Megen, Guido Reiss
      Pages: 3 - 13
      Abstract: The reaction of 1,8-diaminooctane with hydroiodic acid in the presence of iodine gave a new polyiodide-containing salt: 1,8-diaminiumoctane bis(triiodide), (H3N-(CH2)8-NH3)[I3]2. The title compound has been characterized by crystallographic and spectroscopic methods. The polyiodide ion is the first example of a hydrogen bonded I62− dianion consisting of two very asymmetric triiodide components with I−I distances of 2.7739(4) and 3.1778(4) Å interacting by a weak halogen bond (I···I: 3.5017(2) Å). The structural parameters of the triiodide anions, derived from X-ray crystallographic data, are in good agreement with the Raman and Far-IR spectroscopic results.
      PubDate: 2013-10-31
      DOI: 10.3390/inorganics1010003
      Issue No: Vol. 1, No. 1 (2013)
       
  • Inorganics, Vol. 1, Pages 14-31: Amorphous Li-Al-Based Compounds: A Novel
           Approach for Designing High Performance Electrode Materials for Li-Ion
           Batteries

    • Authors: Franziska Thoss, Lars Giebeler, Jürgen Thomas, Steffen Oswald, Kay Potzger, Helfried Reuther, Helmut Ehrenberg, Jürgen Eckert
      Pages: 14 - 31
      Abstract: A new amorphous compound with the initial atomic composition Al43Li43Y6Ni8 applied as electrode material for Li-ion batteries is investigated. Unlike other amorphous compounds so-far investigated as anode materials, it already contains Li as a base element in the uncycled state. The amorphous compound powder is prepared by high energy ball milling of a master alloy. It shows a strongly enhanced specific capacity in contrast to amorphous alloys without Li in the initial state. Therewith, by enabling a reversible (de)lithiation of metallic electrodes without the phase transition caused volume changes it offers the possibility of much increased specific capacities than conventional graphite anodes. According to the charge rate (C-rate), the specific capacity is reversible over 20 cycles at minimum in contrast to conventional crystalline intermetallic phases failing by volume changes. The delithiation process occurs quasi-continuously over a voltage range of nearly 4 V, while the lithiation is mainly observed between 0.1 V and 1.5 V. That way, the electrode is applicable for different potential needs. The electrode stays amorphous during cycling, thus avoiding volume changes. The cycling performance is further enhanced by a significant amount of Fe introduced as wear debris from the milling tools, which acts as a promoting element.
      PubDate: 2013-11-18
      DOI: 10.3390/inorganics1010014
      Issue No: Vol. 1, No. 1 (2013)
       
  • Inorganics, Vol. 1, Pages 32-45: Facile and Selective Synthetic Approach
           for Ruthenium Complexes Utilizing a Molecular Sieve Effect in the
           Supporting Ligand

    • Authors: Dai Oyama, Ayumi Fukuda, Takashi Yamanaka, Tsugiko Takase
      Pages: 32 - 45
      Abstract: It is extremely important for synthetic chemists to control the structure of new compounds. We have constructed ruthenium-based mononuclear complexes with the tridentate 2,6-di(1,8-naphthyridin-2-yl)pyridine (dnp) ligand to investigate a new synthetic approach using a specific coordination space. The synthesis of a family of new ruthenium complexes containing both the dnp and triphenylphosphine (PPh3) ligands, [Ru(dnp)(PPh3)(X)(L)]n+ (X = PPh3, NO2−, Cl−, Br−; L = OH2, CH3CN, C6H5CN, SCN−), has been described. All complexes have been spectroscopically characterized in solution, and the nitrile complexes have also been characterized in the solid state through single-crystal X-ray diffraction analysis. Dnp in the present complex system behaves like a “molecular sieve” in ligand replacement reactions. Both experimental data and density functional theory (DFT) calculations suggest that dnp plays a crucial role in the selectivity observed in this study. The results provide useful information toward elucidating this facile and selective synthetic approach to new transition metal complexes.
      PubDate: 2013-12-09
      DOI: 10.3390/inorganics1010032
      Issue No: Vol. 1, No. 1 (2013)
       
  • Inorganics, Vol. 1, Pages 46-69: Synthesis and Characterisation of
           Lanthanide N-Trimethylsilyl and -Mesityl Functionalised
           Bis(iminophosphorano)methanides and -Methanediides

    • Authors: George Marshall, Ashley Wooles, David Mills, William Lewis, Alexander Blake, Stephen Liddle
      Pages: 46 - 69
      Abstract: We report the extension of the series of {BIPMTMSH}− (BIPMR = C{PPh2NR}2, TMS = trimethylsilyl) derived rare earth methanides by the preparation of [Ln(BIPMTMSH)(I)2(THF)] (Ln = Nd, Gd, Tb), 1a–c, in 34–50% crystalline yields via the reaction of [Ln(I)3(THF)3.5] with [Cs(BIPMTMSH)]. Similarly, we have extended the range of {BIPMMesH}− (Mes = 2,4,6-trimethylphenyl) derived rare earth methanides with the preparation of [Gd(BIPMMesH)(I)2(THF)2], 3, (49%) and [Yb(BIPMMesH)(I)2(THF)], 4, (26%), via the reaction of [Ln(I)3(THF)3.5] with [{K(BIPMMesH)}2]. Attempts to prepare dysprosium and erbium analogues of 3 or 4 were not successful, with the ion pair species [Ln(BIPMMesH)2][BIPMMesH] (Ln  = Dy, Er), 5a–b, isolated in 31–39% yield. The TMEDA (N',N',N",N"-tetramethylethylenediamine) adducts [Ln(BIPMMesH)(I)2(TMEDA)] (Ln = La, Gd), 6a–b, were prepared in quantitative yield via the dissolution of [La(BIPMMesH)(I)2(THF)] or 3 in a TMEDA/THF solution. The reactions of [Ln(BIPMMesH)(I)2(THF)] [Ln  = La, Ce, Pr, and Gd (3)] or 6a–b with a selection of bases did not afford [La(BIPMMes)(I)(S)n] (S = solvent) as predicted, but instead led to the isolation of the heteroleptic complexes [Ln(BIPMMes)(BIPMMesH)] (Ln = La, Ce, Pr and Gd), 7a–d, in low yields due to ligand scrambling.
      PubDate: 2013-12-12
      DOI: 10.3390/inorganics1010046
      Issue No: Vol. 1, No. 1 (2013)
       
  • Inorganics, Vol. 1, Pages 70-84: Synthesis of Diazonium
           Tetrachloroaurate(III) Precursors for Surface Grafting

    • Authors: Sabine Neal, Samuel Orefuwa, Atiya Overton, Richard Staples, Ahmed Mohamed
      Pages: 70 - 84
      Abstract: The synthesis of diazonium tetrachloroaurate(III) complexes [R-4-C6H4N≡N]AuCl4 involves protonation of anilines CN-4-C6H4NH2, C8F17-4-C6H4NH2, and C6H13-4-C6H4NH2 with tetrachloroauric acid H[AuCl4] 3H2O in acetonitrile followed by one-electron oxidation using [NO]PF6. FT-IR shows the diazonium stretching frequency at 2277 cm−1 (CN), 2305 cm−1 (C8F17), and 2253 cm−1 (C6H13). Thermogravimetric Analysis (TGA) shows the high stabilities of the electron-withdrawing substituents C8F17 and CN compared with the electron-donating substituent C6H13. Residual Gas Analysis (RGA) shows the release of molecular nitrogen as the main gas residue among other small molecular weight chlorinated hydrocarbons and chlorobenzene. Temperature-Dependent X-Ray Powder Diffraction (TD-XRD) shows the thermal decomposition in C6H13 diffraction patterns at low temperature of 80 °C which supports the TGA and RGA (TGA-MS) conclusions. X-ray structure shows N≡N bond distance of approximately 1.10 Å and N≡N-C bond angle of 178°.
      PubDate: 2013-12-17
      DOI: 10.3390/inorganics1010070
      Issue No: Vol. 1, No. 1 (2013)
       
 
 
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