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  • CO2 reduction using oxynitrides and nitrides under visible light
    Prog. Solid State Chem. (IF 9.313) Pub Date : 2017-11-22
    Kazuhiko Maeda

    Reduction of CO2 using a heterogeneous photocatalyst under visible light has been studied as a potential means to address the problems of global warming and the depletion of fossil fuels. Recently, hybrid photocatalysts constructed with a metal complex and a particulate semiconductor are of particular interest because of the excellent electrochemical (and/or photocatalytic) ability of the metal complexes for CO2 reduction and the high efficiency of the semiconductors for oxidation reactions, where the ultimate target of oxidation reaction is water oxidation to form molecular O2. This review article highlights our recent progress in the development of metal-complex/semiconductor hybrid materials for visible-light CO2 reduction with a focus on oxynitride and nitride materials as the semiconductor component.

    更新日期:2018-11-29
  • Nitride and oxynitride phosphors for white LEDs: Synthesis, new phosphor discovery, crystal structure
    Prog. Solid State Chem. (IF 9.313) Pub Date : 2017-11-14
    Takashi Takeda, Rong-Jun Xie, Takayuki Suehiro, Naoto Hirosaki

    Si,Al containing nitride and oxynitride phosphors have been applied to white LEDs. Phosphors play important roles to produce high color rendering in lighting and wide color gamut in display. Si,Al containing nitrides and oxynitrides have been studied as high-temperature materials with high strength and thermal shock resistance. The inherited high temperature property is utilized as low thermal quenching in luminescence. The increased covalent bonding character compared to oxide phosphors contributes to high efficiency in blue excitation. The crystal structure (especially the coordination sphere around luminescent center) dominates the luminescent property of phosphor. Wide variety of crystal structure in Si,Al containing nitride and oxynitride leads to multiplicity of luminescent property. In this contribution, Si,Al containing nitride and oxynitride phosphors are reviewed from viewpoints of synthesis, new phosphor discovery, and crystal structure.

    更新日期:2018-11-29
  • Synthetic approaches in oxynitride chemistry
    Prog. Solid State Chem. (IF 9.313) Pub Date : 2017-11-03
    Amparo Fuertes

    Mixed anion oxides are emerging materials showing a variety of physical and chemical properties. Among them oxynitrides are widely investigated because of notable photocatalytic, dielectric, luminescent and electronic properties. Nitrides show more positive free energies of formation than oxides because of the higher stability of N2 molecule with respect to O2 and the unfavourable electron affinity of nitrogen compared to oxygen. However the stability of oxynitrides is higher than for nitrides, and they easily form from oxides in presence of reactive gases as NH3. In addition to ammonolysis several synthetic strategies have been developed in the last years leading to the stabilization of relevant materials with a variety of structures. In this review we will discuss recent progress in the synthesis of oxynitrides emphasizing the importance of kinetic factors and the influence of preparative parameters on the structure types and oxidation states of the cations, and the consequences on physical properties.

    更新日期:2018-11-29
  • Magnetic iron nitrides inspired by historic research on α″-Fe16N2
    Prog. Solid State Chem. (IF 9.313) Pub Date : 2017-06-06
    Shinichi Kikkawa, Yuji Masubuchi

    Strong ferromagnetic materials at room temperature are of interest for various magnetic applications such as magnetic recording, sensors, and motors. Gigantic magnetism expected for α″-Fe16N2 thin films had been attracted much attention in terms of its large magnetization per weight in comparison to rare earth iron nitrides R2Fe17N3 because these films are made of only iron and nitrogen. It developed much straggling on iron nitride thin film research but inconsistent results were obtained using different preparation methods. A powdered α″-Fe16N2-like compound was prepared by the ammonolysis of fine α-Fe powder in low temperature below 200 °C to clarify the confusion; the magnetism was not large in α″-Fe16N2 itself but was increased in the intermediate ammonolysis dual-phase mixture product of the α″-Fe16N2-like compound and residual α-Fe. A way to control the magnetic coercivity was subsequently investigated to utilize the larger magnetization in the α″-Fe16N2-like compound mixture as magnetic materials similarly to Sm2Fe17N3 bonded magnet. Iron nitrides, zinc blende type γ″-FeN and rock-salt type γ‴-FeN, also decompose at around 500 °C. Thermal decomposition was a disadvantage in the preparation of the iron nitrides; however, iron nanoparticles dispersed composites in AlN matrix were derived from the iron nitrides (Fe,Al)N by thermal treatment including laser heating. Iron nitrides are thus promising magnetic materials for their potential applications in science and technology.

    更新日期:2018-11-29
  • Itinerant nitrides and salt-like guanidinates – The diversity of solid-state nitrogen chemistry
    Prog. Solid State Chem. (IF 9.313) Pub Date : 2017-04-05
    Tanja Scholz, Arno L. Görne, Richard Dronskowski

    Recent advances in the chemistry of two peculiar nitrogen-based materials, that is, ternary itinerant iron nitrides and unsubstituted guanidinate salts, are reviewed. Key to their synthesis is the versatile tool ammonia, either as a gas or as a liquid. For metallic nitrides MxFe4−xN including transition-metal and main-group elements M, it is of paramount importance to follow an improved ammonolytic reaction for achieving both stable and metastable compounds; in addition, there is a magnetic effect acting on the crystal structure of GaxFe4−xN, and one also finds spin-glass behavior in main-group nitrides (M = Ga, Ge, Sn). The guanidinate review features an oxidation-controlled low-temperature synthesis of Yb salts, the first magnetic guanidinates, and the doubly-deprotonated guanidinates; the latter represent the all-nitrogen analogues of the ubiquitous carbonates. The covered guanidinates adopt the compositions MCN3H4, M(CN3H4)2, M(CN3H4)3 and MC(NH)3 (M = Li–Cs, Sr, Eu, Yb). We also cover the application of first-principles calculations at all levels to gain a deeper understanding of the studied materials.

    更新日期:2018-11-29
  • Remarkable effects of local structure in tantalum and niobium oxynitrides
    Prog. Solid State Chem. (IF 9.313) Pub Date : 2017-08-24
    Shinichi Kikkawa, Akira Hosono, Yuji Masubuchi

    Compounds that contain two types of anion are attracting attention as a new field of solid state chemistry. The nitride anion is similar to the oxide anion in size and nature. They coordinate together to cations in oxynitrides to form characteristic local structures around them in a certain way. Special properties induced by the specific local structure have been observed in oxynitrides. Ferroelectricity was identified in oxynitride perovskites, especially those of tantalum, because the oxide and nitride anions form a polar ordered local crystal structure around Ta5+ in the 5d0 electron configuration. The critical current density in superconductivity was enhanced by the formation of clusters in niobium oxynitrides with the rocksalt-type structure. Main group elements doped into the niobium oxynitrides, especially silicon, are coordinated mainly by oxides with some amount of nitrides to form silicon oxide-like clusters. The niobium in the oxynitride has some 4d electrons to maintain the superconductivity in the niobium oxynitride host. Here, the preparation, crystal structure and properties of oxynitrides formed with tantalum and niobium are reviewed.

    更新日期:2018-11-29
  • Sodium flux synthesis of nitrides
    Prog. Solid State Chem. (IF 9.313) Pub Date : 2017-09-14
    Hisanori Yamane, Francis J. DiSalvo

    Studies of the synthesis of solid state nitrides using a Na flux are reviewed. The role and effect of Na is to solubilize polyatomic species containing nitrogen, and to lower the crystal growth temperature below the decomposition temperature of the obtained product(s). Many new ternary and quaternary nitrides have been synthesized in single crystal forms with sizes at least large enough (or larger) than is needed for structure analysis by X-ray diffraction. Isolated and extended anionic groups typically containing N and Si, Ge, Ga, and/or some transition metal elements are typical. These are usually surrounded by alkaline-earth atoms and are the most common of such nitrides. Compounds composed of nitridometallate anions and Zintl polyanions are also obtained. The structural features of each of these compounds are described.

    更新日期:2018-11-29
  • Mixed ternary transition metal nitrides: a comprehensive review of synthesis, electronic structure, and properties of engineering relevance
    Prog. Solid State Chem. (IF 9.313) Pub Date : 2018-11-28
    Ayesha Khan Tareen, G. Sudha Priyanga, Santosh Behara, Tiju Thomas, Minghui Yang

    Ternary transition metal nitrides (TTMNs) have acquired substantial attention due to the ability to offer for tuning properties. Furthermore efforts to develop new TTMNs have resulted in the development of new syntheses approaches. In this review, recent progress made regarding investigations on electronic structure, stoichiometry, crystal structures, synthesis and applications are reviewed. Intermediate bonding in these solids exist in the structure types revealed so far. Bonding in these systems are an intriguing mix of ionic (oxide-like) and covalent (carbide-like). This enhances the possibilities of finding unique structures (i.e. anti-fluorite analogous1). A good case in point is the Delafosite types and η-nitrides structures found commonly in TTMNs which are typically associated with ABOx type oxides and carbides. Due to the rich structural chemistry associated with TTMNs, their study is considered a growing area in solid state and applied chemistry. Advancement made in the synthesis of powder and thin film materials of TTMNs are discussed. The powder methods involve the following methods: solid state, high-pressure-high temperature, solvothermal method, ammonothermal method, sol-gel method, Pechini method, temperature-programmed reduction, thermal degradation of metal complex, solid-state metal oxide-organic reaction, solid state ion exchange reaction, and electrodeposition replacement method. On the other hand, the TTMN thin film fabrication is based on two types of methods; physical vapor deposition (PVD) and chemical vapor deposition (CVD) method. The PVD involve deposition using different ways using laser or plasma based approaches (eg. pulsed laser deposition (PLD)) and magnetron sputtering. Chemical vapor deposition methods involve electrodeposition reaction method. Among all synthesis methods, the sol-gel process following the ammonolysis is considered comparatively better for large scale production owing to the simple apparatus setup. Different synthesis methods are deployable based on the application at hand. Applications can be range from electrocatalysts in ORR reaction2,3, electrocatalysts as sensor4, supercapacitors2,3,5, solar cell6, magnetic, superconducting7, hard coating materials8 e.g. protective, functional, conductive, wear-resistance and decorative coating, NH3 synthesis9, and hydrogenation process in hydrocarbon reactions.10

    更新日期:2018-11-28
  • The complex nonstoichiometry of wüstite Fe 1-z O: review and comments
    Prog. Solid State Chem. (IF 9.313) Pub Date : 2018-10-13
    Jean-Raymond Gavarri, Claude Carel

    Thermodynamic properties and structural aspects of the nonstoichiometric wüstite Fe1-zO, and its modifications - the so-called pseudo-phases - as functions of departure z from stoichiometry and of equilibrium temperature are reviewed from 1960 to present. The complexity of the equilibrium phase diagram is described in some details. The first order transition W ⇆ W’ is specified on the iron/wüstite boundary near 1185 K. Transitions correlated to the modifications Wi at T(W) > 1185 K and W’j at T(W’) < 1185 K (i and j =1,2,3) are re-examined. Structural determinations based on the characterization of point defects stabilization and of their clustering are reviewed. Additionally, the pseudo-phases are examined based on the transformation of defect clusters or of their mode of distribution (i.e., percolation or superstructure) with the inclusion of changes in electronic charge carriers.

    更新日期:2018-10-14
  • 更新日期:2018-09-12
Some contents have been Reproduced with permission of the American Chemical Society.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
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