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Inorganics
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Novel Solid-State Nitride Materials
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Novel Solid-State Nitride Materials

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Inorganic Solid-State Chemistry".

Deadline for manuscript submissions: closed (30 September 2016) | Viewed by 34854

Special Issue Editor

Prof. Dr. Rainer Niewa

E-Mail Website
Guest Editor
Institut für Anorganische Chemie, Universität Stuttgart, 70569 Stuttgart, Germany
Interests: solid state chemistry; materials chemistry; synthesis; crystal growth; structure-property relationships
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Nitrides, a few of which are even known to occur in nature, have attracted a huge and ever-increasing interest from scientists coming from broadly different scientific communities. Even though nitride chemistry shares to some extent similarities with oxides, in particular the unfavorable electron affinity and high dissociation energy of nitrogen highlight these differences: They lead not only to comparably low thermal stabilities and small band gaps, but also to a completely new structural and redox chemistry, as well as physics. Solid solutions of nitrides and oxides allow to precisely controlling properties as, for example, band gap sizes and band edge positions. Within the past decades, nitride chemistry has emerged into a fruitful area of research nowadays covering widely different disciplines, such as synthetic and structural chemistry, physics, materials research and theoretical chemistry. The large variety of highly attractive combinations of properties, such as high magnetic moments, luminescence, ionic or electric conductivity, versatile redox and catalytic properties, excellent chemical stability or high hardness, to name only a few, provide innumerable possibilities for novel applications and devices. At the same time the still underexplored materials class of nitrides in general offers a broad spectrum of opportunities for basic explorative chemistry, as well as new and exciting physics and properties investigation. The main focus of this Special Issue is on the latest advances made in nitride chemistry. These advances cover novel synthetic techniques, structure and property determination and possible applications in all fields of chemistry, physics and beyond.

Prof. Dr. Rainer Niewa
Guest Editor

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Keywords

  • synthesis and characterization techniques
  • high pressure and temperature synthesis
  • mechanical properties
  • magnetism and transport properties
  • catalysis, photocatalysis and water splitting
  • energy storage and conversion
  • electronic structure studies

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Published Papers (6 papers)

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Research

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13 pages, 10190 KiB  
Article
Influence of Fatty Acid Alkyl Chain Length on Anisotropy of Copper Nitride Nano-Crystallites
by Takashi Nakamura
Inorganics 2017, 5(1), 6; https://doi.org/10.3390/inorganics5010006 - 16 Jan 2017
Cited by 1 | Viewed by 6739
Abstract
My group developed a simple method to prepare copper nitride fine particles from copper carboxylate in a solvent of long-chain alcohols without the use of high temperatures or high pressures. By selecting copper acetate or copper decanoate as the copper source, my group [...] Read more.
My group developed a simple method to prepare copper nitride fine particles from copper carboxylate in a solvent of long-chain alcohols without the use of high temperatures or high pressures. By selecting copper acetate or copper decanoate as the copper source, my group demonstrated that the morphology of the copper nitride fine particles varied between cubic and plate-like, respectively. Although a hypothesis was proposed to explain the influence of the length of the alkyl chain on the copper decanoate, it is uncertain how much the chain length influences the shape of the fine particles. In this work, I demonstrated the effect of the length of the alkyl chain on particle shape by preparing fine particles from a series of copper sources with different alky chain lengths and characterizing the particles with x-ray diffractometry (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The main findings were as follows: (1) the fine particles were plate-like when the alkyl chain length exceeded 5; (2) the aspect ratio of the plate-like particles increased as the alkyl chain length increased; and (3) growth of the (110) and (111) planes of the copper nitride crystal were selectively inhibited. Full article
(This article belongs to the Special Issue Novel Solid-State Nitride Materials)
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10 pages, 1918 KiB  
Article
The A-Type Ln4N2S3 Series: New Nitride Sulfides of the Light Lanthanoids (Ln = Ce–Nd)
by Falk Lissner and Thomas Schleid
Inorganics 2017, 5(1), 2; https://doi.org/10.3390/inorganics5010002 - 23 Dec 2016
Cited by 4 | Viewed by 5111
Abstract
The reaction of lanthanoid metal powders (Ln) with sulfur and cesium azide (CsN3) as a nitrogen source in the presence of lanthanoid tribromides (LnBr3) yields lanthanoid nitride sulfides with the composition Ln4N2 [...] Read more.
The reaction of lanthanoid metal powders (Ln) with sulfur and cesium azide (CsN3) as a nitrogen source in the presence of lanthanoid tribromides (LnBr3) yields lanthanoid nitride sulfides with the composition Ln4N2S3 (Ln = Ce–Nd) when appropriate molar ratios of the starting material are used. Additional cesium bromide (CsBr) as a flux secures quantitative conversion (7 days) at 900 °C in evacuated silica tubes as well as the formation of black single crystals. All compounds crystallize isotypically with the orthorhombic crystal structure of La4N2S3 (Pnnm, Z = 2) and their structures were determined from single-crystal X-ray diffraction data (Ce4N2S3: a = 644.31(4), b = 1554.13(9), c = 404.20(3) pm; Pr4N2S3: a = 641.23(4), b = 1542.37(9), c = 400.18(3) pm; Nd4N2S3: a = 635.19(4), b = 1536.98(9), c = 397.85(3) pm). Compared to La4N2S3 the a-axes do not fulfill the expectation of the lanthanide contraction. The main feature of the crystal structure comprises N3−-centered (Ln3+)4 tetrahedra arranging as pairs [N2Ln6]12+ of edge-shared [NLn4]9+ units, which are further connected via four vertices to form double chains ∞ 1{([NLn4/2]2)6+}. Bundled along [001] like a hexagonal rod packing, they are held together by two crystallographically different S2− anions. Two compounds of a second modification (B-type La4N2S3 and Pr4N2S3) will also be presented and discussed for comparison. Full article
(This article belongs to the Special Issue Novel Solid-State Nitride Materials)
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10 pages, 1240 KiB  
Article
Single Crystal Growth and Anisotropic Magnetic Properties of Li2Sr[Li1 − xFexN]2
by Peter Höhn, Tanita J. Ballé, Manuel Fix, Yurii Prots and Anton Jesche
Inorganics 2016, 4(4), 42; https://doi.org/10.3390/inorganics4040042 - 21 Dec 2016
Cited by 14 | Viewed by 5682
Abstract
Up to now, investigation of physical properties of ternary and higher nitridometalates has been severely hampered by challenges concerning phase purity and crystal size. Employing a modified lithium flux technique, we are now able to prepare sufficiently large single crystals of the highly [...] Read more.
Up to now, investigation of physical properties of ternary and higher nitridometalates has been severely hampered by challenges concerning phase purity and crystal size. Employing a modified lithium flux technique, we are now able to prepare sufficiently large single crystals of the highly air and moisture sensitive nitridoferrate Li 2 Sr[Li 1 − x Fe x N] 2 for anisotropic magnetization measurements. The magnetic properties are most remarkable: large anisotropy and coercivity fields of 7 Tesla at T = 2 K indicate a significant orbital contribution to the magnetic moment of iron. Altogether, the novel growth method opens a route towards interesting phases in the comparatively recent research field of nitridometalates and should be applicable to various other materials. Full article
(This article belongs to the Special Issue Novel Solid-State Nitride Materials)
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9 pages, 2289 KiB  
Article
Synthesis and Structure Determination of the Quaternary Zinc Nitride Halides Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1)
by Yanqing Li, Xiaohui Liu and Richard Dronskowski
Inorganics 2016, 4(4), 29; https://doi.org/10.3390/inorganics4040029 - 29 Sep 2016
Cited by 1 | Viewed by 5604
Abstract
The quaternary series Zn2NCl1−yBry and Zn2NBr1−yIy were synthesized from solid-liquid reactions between zinc nitride and the respective zinc halides in closed ampoules, and the evolution of their crystal structures was investigated [...] Read more.
The quaternary series Zn2NCl1−yBry and Zn2NBr1−yIy were synthesized from solid-liquid reactions between zinc nitride and the respective zinc halides in closed ampoules, and the evolution of their crystal structures was investigated by single-crystal and powder X-ray diffraction. Zn2NX1−yX′y (X, X′ = Cl, Br, I) adopts the anti-β-NaFeO2 motif in which each nitride ion is tetrahedrally coordinated by four zinc cations, and the halide anions are located in the voids of the skeleton formed by corner-sharing [NZn4] tetrahedra. While Zn2NCl1−yBry crystallizes in the acentric orthorhombic space group Pna21 (No. 33), isotypic to Zn2NX (X = Cl, Br), the structure of Zn2NBr1−yIy is a function of the iodide concentration, namely, Zn2NBr (Pna21) for low iodine content and Zn2NI (Pnma) for higher (y ≥ 0.38). Full article
(This article belongs to the Special Issue Novel Solid-State Nitride Materials)
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10 pages, 2740 KiB  
Article
Mesoporous WN/WO3-Composite Nanosheets for the Chemiresistive Detection of NO2 at Room Temperature
by Fengdong Qu, Bo He, Rohiverth Guarecuco and Minghui Yang
Inorganics 2016, 4(3), 24; https://doi.org/10.3390/inorganics4030024 - 26 Jul 2016
Cited by 9 | Viewed by 5742
Abstract
Composite materials, which can optimally use the advantages of different materials, have been studied extensively. Herein, hybrid tungsten nitride and oxide (WN/WO3) composites were prepared through a simple aqueous solution route followed by nitriding in NH3, for application as [...] Read more.
Composite materials, which can optimally use the advantages of different materials, have been studied extensively. Herein, hybrid tungsten nitride and oxide (WN/WO3) composites were prepared through a simple aqueous solution route followed by nitriding in NH3, for application as novel sensing materials. We found that the introduction of WN can improve the electrical properties of the composites, thus improving the gas sensing properties of the composites when compared with bare WO3. The highest sensing response was up to 21.3 for 100 ppb NO2 with a fast response time of ~50 s at room temperature, and the low detection limit was 1.28 ppb, which is far below the level that is immediately dangerous to life or health (IDLH) values (NO2: 20 ppm) defined by the U.S. National Institute for Occupational Safety and Health (NIOSH). In addition, the composites successfully lower the optimum temperature of WO3 from 300 °C to room temperature, and the composites-based sensor presents good long-term stability for NO2 of 100 ppb. Furthermore, a possible sensing mechanism is proposed. Full article
(This article belongs to the Special Issue Novel Solid-State Nitride Materials)
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Review

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17 pages, 7637 KiB  
Review
Structural Classification of Quasi-One-Dimensional Ternary Nitrides
by David Andrew Headspith and Maria Grazia Francesconi
Inorganics 2016, 4(4), 37; https://doi.org/10.3390/inorganics4040037 - 30 Nov 2016
Cited by 5 | Viewed by 5130
Abstract
This review focuses on the crystal structural features of ternary (mixed-metal) quasi-one-dimensional nitrides i.e., nitrides containing (cation-N3−) coordination polyhedra sharing either corners, edges, or faces, arranged in linear chains, and intercalated by a counter ion. The current relevance of these nitrides, [...] Read more.
This review focuses on the crystal structural features of ternary (mixed-metal) quasi-one-dimensional nitrides i.e., nitrides containing (cation-N3−) coordination polyhedra sharing either corners, edges, or faces, arranged in linear chains, and intercalated by a counter ion. The current relevance of these nitrides, and of quasi-one-dimensional compounds in general, lies in the fact that they are closely related to the pure one-dimensional systems (i.e., nanowires), which are vastly researched for their amazing properties closely related to their low dimensionality. A number of these properties were firstly discovered in quasi-one-dimensional compounds, highlighting the importance of expanding knowledge and research in this area. Furthermore, unlike oxides, nitrides and other non-oxide compounds are less developed, hence more difficult to categorise into structural classes that can then be related to other classes of compounds, leading to a fuller picture of structure–properties relationship. Within this context, this review aims to categorise and describe a number of ternary (mixed-metal) quasi-one-dimensional nitrides according to their structural features, specifically, the polyhedra forming the one-dimensional chains. Full article
(This article belongs to the Special Issue Novel Solid-State Nitride Materials)
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