Nitrogen Photofixation over III‐Nitride Nanowires Assisted by Ruthenium Clusters of Low Atomicity

In many heterogeneous catalysts, the interaction of supported metal species with a matrix can alter the electronic and morphological properties of the metal and manipulate its catalytic properties. III‐nitride semiconductors have a unique ability to stabilize ultra‐small ruthenium (Ru) clusters (ca. 0.8 nm) at a high loading density up to 5 wt %. n‐Type III‐nitride nanowires decorated with Ru sub‐nanoclusters offer controlled surface charge properties and exhibit superior UV‐ and visible‐light photocatalytic activity for ammonia synthesis at ambient temperature. A metal/semiconductor interfacial Schottky junction with a 0.94 eV barrier height can greatly facilitate photogenerated electron transfer from III‐nitrides to Ru, rendering Ru an electron sink that promotes N≡N bond cleavage, and thereby achieving low‐temperature ammonia synthesis.     

United in Nitride: The Highly Condensed Boron Phosphorus Nitride BP3N6

Owing to intriguing materials properties non‐metal nitrides are of special interest for both, solid‐state chemistry and materials science. Mixed ternary non‐metal nitrides, however, have only been sparsely investigated, as preparative chemistry lacks a systematic access, yet. Herein, we report on the highly condensed boron phosphorus nitride BP₃N₆, which was synthesized from (PNCl₂)₃, NH₄N₃ and h‐BN in a high‐pressure high‐temperature reaction. By increasing partial pressure of HCl during synthesis using NH₄Cl, single‐crystals of BP₃N₆ up to 80 μm in length were obtained. The unprecedented framework‐type structure determined by single‐crystal XRD blends structural motifs of both, α‐P₃N₅ and c‐BN, rendering BP₃N₆ a double nitride. The compound was further investigated by Rietveld refinement, EDX, temperature‐dependent PXRD, FTIR and solid‐state NMR spectroscopy. The formation of BP₃N₆ through use of reactive precursors exemplifies an innovative access to mixed non‐metal nitrides.     

N−H Bond Formation at a Diiron Bridging Nitride

Despite their connection to ammonia synthesis, little is known about the ability of iron‐bound, bridging nitrides to form N?H bonds. Herein we report a linear diiron bridging nitride complex supported by a redox‐active macrocycle. The unique ability of the ligand scaffold to adapt to the geometric preference of the bridging species was found to facilitate the formation of N?H bonds via proton‐coupled electron transfer to generate a μ‐amide product. The structurally analogous μ‐silyl‐ and μ‐borylamide complexes were shown to form from the net insertion of the nitride into the E?H bonds (E=B, Si). Protonation of the parent bridging amide produced ammonia in high yield, and treatment of the nitride with PhSH was found to liberate NH₃ in high yield through a reaction that engages the redox‐activity of the ligand during PCET.     

Rivalry under Pressure: The Coexistence of Ambient‐Pressure Motifs and Close‐Packing in Silicon Phosphorus Nitride Imide SiP2N4NH

Non‐metal nitrides such as BN, Si₃N₄, and P₃N₅ meet numerous demands on high‐performance materials, and their high‐pressure polymorphs exhibit outstanding mechanical properties. Herein, we present the silicon phosphorus nitride imide SiP₂N₄NH featuring sixfold coordinated Si. Using the multi‐anvil technique, SiP₂N₄NH was obtained by high‐pressure high‐temperature synthesis at 8 GPa and 1100 °C with in situ formed HCl acting as a mineralizer. Its structure was elucidated by a combination of single‐crystal X‐ray diffraction and solid‐state NMR measurements. Moreover, SiP₂N₄NH was characterized by energy‐dispersive X‐ray spectroscopy and (temperature‐dependent) powder X‐ray diffraction. The highly condensed Si/P/N framework features PN₄ tetrahedra as well as the rare motif of SiN₆ octahedra, and is discussed in the context of ambient‐pressure motifs competing with close‐packing of nitride anions, representing a missing link in the high‐pressure chemistry of non‐metal nitrides.     

The structure and reactivity of iron nitride complexes

The structure and reactivity of discrete iron nitride complexes is described. Six-coordinate, four-fold symmetric nitrides are thermally unstable, and have been characterized at cryogenic temperatures by an arsenal of spectroscopic methods. By contrast, four-coordinate, three-fold symmetric iron nitrides can be prepared at room temperature. A range of diamagnetic iron(IV) nitrides have been reported and in some cases, isolated. Among these are the isolable, yet reactive, tris(carbene)borate iron(IV) nitrides. These complexes can effect two-electron nitrogen atom transfer to a range of substrates, in some cases with complete atom transfer occuring through Fe-N bond cleavage. These nitrides are also active in single electron pathways, including the synthesis of ammonia by a mechanism involving hydrogen atom transfer to the nitride ligand. One-electron oxidation of a tris(carbene)borate iron(IV) nitride leads to an isolable iron(V) complex that is unusually reactive for a metal nitride.     

A Low‐Valent Molybdenum Nitride Complex: Reduction Promotes Carbonylation Chemistry

Toward nitrogen functionalization, reactive terminal transition metal nitrides with high d‐electron counts are of interest. A series of terminal Mo^IV nitride complexes were prepared within the context of exploring nitride/carbonyl coupling to cyanate. Reduction affords the first Mo^II nitrido complex, an early metal nitride with four valence d‐electrons. The binding mode of the para‐terphenyl diphosphine ancillary ligand changes to stabilize an electronic configuration with a high electron count and a formal M?N bond order of three. Even with an intact Mo≡N bond, this low‐valent nitrido complex proves to be highly reactive, readily undergoing N‐atom transfer upon addition of CO, releasing cyanate anion.     

A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity

Low‐valent osmium nitrides are discussed as intermediates in nitrogen fixation schemes. However, rational synthetic routes that lead to isolable examples are currently unknown. Here, the synthesis of the square‐planar osmium(IV) nitride [OsN(PNP)] (PNP=N(CH₂CH₂P(tBu)₂)₂) is reported upon reversible deprotonation of osmium(VI) hydride [Os(N)H(PNP)]⁺. The Os^IV complex shows ambiphilic nitride reactivity with SiMe₃Br and PMe₃, respectively. Importantly, the hydrogenolysis with H₂ gives ammonia and the polyhydride complex [OsH₄(HPNP)] in 80 % yield. Hence, our results directly demonstrate the role of low‐valent osmium nitrides and of heterolytic H₂ activation for ammonia synthesis with H₂ under basic conditions.     

Boron Phosphorus Nitride at Extremes: PN6 Octahedra in the High‐Pressure Polymorph β‐BP3N6

The high‐pressure behavior of non‐metal nitrides is of special interest for inorganic and theoretical chemistry as well as materials science, as these compounds feature intriguing elastic properties. The double nitride α‐BP₃N₆ was investigated by in situ single‐crystal X‐ray diffraction (XRD) upon cold compression to a maximum pressure of about 42 GPa, and its isothermal bulk modulus at ambient conditions was determined to be 146(6) GPa. At maximum pressure the sample was laser‐heated, which resulted in the formation of an unprecedented high‐pressure polymorph, β‐BP₃N₆. Its structure was elucidated by single‐crystal XRD, and can be described as a decoration of a distorted hexagonal close packing of N with B in tetrahedral and P in octahedral voids. Hence, β‐BP₃N₆ is the first nitride to contain PN₆ octahedra, representing the much sought‐after proof of principle for sixfold N‐coordinated P that has been predicted for numerous high‐pressure phases of nitrides.     

Endohedral clusterfullerenes--playing with cluster and cage sizes

The family of endohedral fullerenes was significantly enlarged within the past six years by the clusterfullerenes containing structures like the M(2)C(2) carbides and the M(3)N nitrides. While the carbide clusters are generated under the standard arc burning conditions according to the stabilisation energy the nitride clusterfullerene type is formed by varying the composition of the cooling gas atmosphere in the arc burning process. The special situation in nitride clusterfullerene synthesis is described in detail and the optimum conditions for the production of nitride clusterfullerenes as the main product in fullerene synthesis are discussed. A review of new nitride clusterfullerenes reported recently is given summarizing the structures, properties and the stability of metal nitride clusterfullerenes. It is shown that all cages with even carbon atoms of C(68) and beyond are available as endohedral nitride clusterstructures. Furthermore the nitride clusterfullerenes are that class of endohedral fullerenes forming the largest number of non-IPR structures. Finally the prospects of this evolving field are briefly discussed taking the superior stability of these endohedral clusterfullerenes into account.     

Highly Active GaN‐Stabilized Ta3N5 Thin‐Film Photoanode for Solar Water Oxidation

Ta₃N₅ is a very promising photocatalyst for solar water splitting because of its wide spectrum solar energy utilization up to 600 nm and suitable energy band position straddling the water splitting redox reactions. However, its development has long been impeded by poor compatibility with electrolytes. Herein, we demonstrate a simple sputtering‐nitridation process to fabricate high‐performance Ta₃N₅ film photoanodes owing to successful synthesis of the vital TaO_δ precursors. An effective GaN coating strategy is developed to remarkably stabilize Ta₃N₅ by forming a crystalline nitride‐on‐nitride structure with an improved nitride/electrolyte interface. A stable, high photocurrent density of 8 mA cm⁻² was obtained with a CoPi/GaN/Ta₃N₅ photoanode at 1.2 V_RHE under simulated sunlight, with O₂ and H₂ generated at a Faraday efficiency of unity over 12 h. Our vapor‐phase deposition method can be used to fabricate high‐performance (oxy)nitrides for practical photoelectrochemical applications.     

Solid State Metathesis Reactions in Various Applications

Solid state metathesis reactions have been studied in fused silica tubes, by differential thermal analysis, and by X‐ray powder diffraction. A selection of reactions between metal (La, Nb, and Ni) chlorides and lithium nitride or lithium acetylide were investigated to get more insight into reaction pathways and intermediate reaction stages that may be adopted on course of the formation of metal nitrides or carbides. Intermediate compounds are considered to be important because they can control the reactivity of a system. Such compounds were traced by changing the molar ratios of reaction partners away from the salt‐balanced binary metal nitride or carbide target compositions. New preparative perspectives are discovered when metal chlorides were reacted with lithium nitridoborate or lithium cyanamide. Due to their reductive nature towards several d‐block metal chlorides, (BN₂)^3‐ and (CN₂)^2‐ react to form metals or metal nitrides plus X‐ray amorphous BN, and probably C₃N₄. With lanthanum chloride they can react to form nitridoborates and nitridocarbonates. The metathesis reaction between lithium cyanamide and cyanuric chloride (C₃N₃Cl₃) instead of metal chloride was studied for the synthesis of C₃N₄.     

Potassium Poly(Heptazine Imide): Transition Metal‐Free Solid‐State Triplet Sensitizer in Cascade Energy Transfer and [3+2]‐cycloadditions

Polymeric carbon nitride materials have been used in numerous light‐to‐energy conversion applications ranging from photocatalysis to optoelectronics. For a new application and modelling, we first refined the crystal structure of potassium poly(heptazine imide) (K‐PHI)—a benchmark carbon nitride material in photocatalysis—by means of X‐ray powder diffraction and transmission electron microscopy. Using the crystal structure of K‐PHI, periodic DFT calculations were performed to calculate the density‐of‐states (DOS) and localize intra band states (IBS). IBS were found to be responsible for the enhanced K‐PHI absorption in the near IR region, to serve as electron traps, and to be useful in energy transfer reactions. Once excited with visible light, carbon nitrides, in addition to the direct recombination, can also undergo singlet–triplet intersystem crossing. We utilized the K‐PHI centered triplet excited states to trigger a cascade of energy transfer reactions and, in turn, to sensitize, for example, singlet oxygen (¹O₂) as a starting point to synthesis up to 25 different N‐rich heterocycles.     

Interface phenomena in (super)hard nitride nanocomposites: from coatings to bulk materials

Mechanical properties of nanocomposites usually surpass the mechanical properties of their micro-structured and single-crystalline counterparts. This is mainly due to an extremely high density of internal interfaces in nanocomposites like grain, crystallite and phase boundaries. When compared to diamond, carbides and borides, nitrides are of interest because of their high temperature oxidation resistance and compatibility with iron containing alloys. This tutorial review classifies the contributions of various internal interfaces to the hardness of the nanocomposites, and appreciates the outstanding role of partially coherent phase boundaries in the hardness enhancement. With selected examples of transition metal nitrides containing aluminium and silicon as well as of boron nitrides, it is explained how the nanocomposites with partially coherent phase boundaries and thus with enhanced hardness can be synthesised. As the possible ways of the formation of coherent phase boundaries, the local epitaxial growth of phases with limited mutual solubility, the production of supersaturated solid solutions followed by the segregation of elements during the spinodal decomposition and the incomplete phase transformation are discussed. The most important techniques, used for synthesis of nitride nanocomposites, like CVD, PVD, precursor-based methods, mechanical alloying and high-pressure-high-temperature synthesis are briefly reviewed. Besides, a short overview on hardness definitions and hardness measurements is included.     

Solid-State Chemistry with Nonmetal Nitrides

Among the nonmetal nitrides, the polymeric binary compounds BN and Si₃N₄are of particular interest for the development of materials for high-performance applications. The outstanding features of both substances are their thermal, mechanical, and chemical stability, coupled with their low density. Because of their extremely low reactivity, boron and silicon nitride are hardly ever used as starting materials for the preparation of ternary nitrides, but are used primarily in the manufacture of crucibles or other vessels or as insulation materials. The chemistry of ternary and higher nonmetal nitrides that contain electropositive elements and are thus analogous with the oxo compounds such as borates, silicates, phosphates, or sulfates was neglected for many years. Starting from the recent successful preparation of pure P₃N₅, a further binary nonmetal nitride which shows similarities with Si₃N₄ with regard to both its structure and properties, this review deals systematically with the solid-state chemistry of ternary and higher phosphorus(V ) nitrides and the relationship between the various types of structure found in this class of substance and the resulting properties and possible applications. From the point of view of preparative solid-state chemistry the syntheses, structures, and properties of the binary nonmetal nitrides BN, Si₃N₄, and P₃N₅ will be compared and contrasted. The chemistry of the phosphorus(V ) nitrides leads us to expect that other nonmetals such as boron, silicon, sulfur, and carbon will also participate in a rich nitride chemistry, as initial reports indeed indicate.     

Vapor Phase Epitaxy of Nitride Films

GaN and related compounds are very promising materials for developing short wavelength light emitting devices, such as laser diode (LD) and light emitting diode (LED), high temperature and high power electronics. Commercially used nitride materials have been made by vapor phase epitaxy (VPE), including metalorganic vapor phase epitaxy (MOVPE) and hydride vapor phase epitaxy (HVPE). MOVPE is a widely used technique to fabricate semiconductor films. Its precise control of growth process, ability of handling multi large area wafers, and excellent reproducibility make it valuable in large-scale production of electronic and optoelectronic devices. VPE of nitrides has met several critical materials issues. Firstly, a high vapor pressure of nitrogen leads to the lack of bulk crystal of GaN. People have to use heteroepitaxy technique to produce GaN materials and devices, which makes high-density defects in GaN epilayers. Secondly, the high bonding energy of GaN and high stability of NH₃ require a high growth temperature. The high nitrogen vapor pressure at high growth temperature requires enhanced local precursor densities. Additionally, the growth chemistry of VPE of nitride materials is very complicated. Parasitic chemical reactions take place during the VPE growth and degrade the material quality. Finally, the physical process of VPE growth has not been well understood. Optimized production of nitride material is predicated on an understanding of how the film properties are affected by the initial processing sequence. Heteroepitaxy of nitrides is strongly influenced by the initial nucleation and growth sequence.     

Crystalline Carbon Nitride Semiconductors for Photocatalytic Water Splitting

Conjugated carbon nitride (CN) is an emerging and promising semiconductor photocatalyst for water photolysis owing to its unique properties. However, the traditional thermally induced polymerization of N‐containing precursors typically produces melon‐based CN solids with amorphous or semi‐crystalline structures with only moderate photocatalytic performance. Many strategies have been developed to prepare crystalline CNs (CCNs), such as high‐temperature and high‐pressure routes, ionothermal synthesis, and microwave‐assisted synthesis. In this Minireview, we summarize the progress that has been made in the synthesis of CCNs and their application in photocatalytic water splitting reactions. Three kinds of CCNs are mainly discussed according to their polymeric subunits. Challenges associated with CCNs and their future development are also included.     

N−H Bond Formation at a Diiron Bridging Nitride

Despite their connection to ammonia synthesis, little is known about the ability of iron-bound, bridging nitrides to form N−H bonds. Herein we report a linear diiron bridging nitride complex supported by a redox-active macrocycle. The unique ability of the ligand scaffold to adapt to the geometric preference of the bridging species was found to facilitate the formation of N−H bonds via proton-coupled electron transfer to generate a μ-amide product. The structurally analogous μ-silyl- and μ-borylamide complexes were shown to form from the net insertion of the nitride into the E−H bonds (E=B, Si). Protonation of the parent bridging amide produced ammonia in high yield, and treatment of the nitride with PhSH was found to liberate NH₃ in high yield through a reaction that engages the redox-activity of the ligand during PCET.     

Decay of Iron(V) Nitride Complexes By a NN Bond‐Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis

Cryogenically trapped Fe^V nitride complexes with cyclam‐based ligands were found to decay by bimolecular reactions, forming exclusively Fe^II compounds. Characterization of educts and products by Mössbauer spectroscopy, mass spectrometry, and spectroscopy‐oriented DFT calculations showed that the reaction mechanism is reductive nitride coupling and release of dinitrogen (2 Fe^V?N→Fe^II‐N?N‐Fe^II→2 Fe^II+N₂). The reaction pathways, representing an “inverse” of the Haber–Bosch reaction, were computationally explored in detail, also to judge the feasibility of yielding catalytically competent Fe^V(N). Implications for the photolytic cleavage of Fe^III azides used to generate high‐valent Fe nitrides are discussed.     

“114”‐Type Nitrides LnAl(Si4−xAlx)N7Oδ with Unusual [AlN6] Octahedral Coordination

Aluminum–nitrogen six‐fold octahedral coordination, [AlN₆], is unusual and has only been seen in the high‐pressure rocksalt‐type aluminum nitride or some complex compounds. Herein we report novel nitrides LnAl(Si_4−x Al_x)N₇O_δ (Ln=La, Sm), the first inorganic compounds with [AlN₆] coordination prepared via non‐high‐pressure synthesis. Structure refinements of neutron powder diffraction and single‐crystal X‐ray diffraction data show that these compounds crystallize in the hexagonal Swedenborgite structure type with P 6₃mc symmetry where Ln and Al atoms locate in anticuboctahedral and octahedral interstitials, respectively, between the triangular and Kagomé layers of [SiN₄] tetrahedra. Solid‐state NMR data of high‐purity La‐114 powders confirm the unusual [AlN₆] coordination. These compounds are the first examples of the “33‐114” sub‐type in the “114” family. The additional site for over‐stoichiometric oxygen in the structure of 114‐type compounds was also identified.     

Microwave Synthesis of Ternary Nitride Materials

The utility of microwave heating and microwave generated nitrogen plasmas as a synthetic technique toward the synthesis of nitrides is demonstrated. The synthesis of several binary and ternary nitrides, including TiN, AlN, VN, Li₃FeN₂, Li₅TiN₃, and Li₃AlN₂, using either a microwave heating source or a microwave generated nitrogen plasma, are described. Two types of reactions, those between a metal and a nitrogen plasma and those between Li₃N and either a metal or a metal nitride in a microwave heating system are discussed.