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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Preparation of GaN on GaAs (100) substrate by annealing and post-nitridation

Preparation of GaN on GaAs (100) substrate by annealing and post-nitridation process has been studied. X-ray diffraction analysis confirmed the formation β-Ga{sub 2}O{sub 3} phase on annealed substrate. Nitridation of annealed samples resulted in formation hexagonal structure of GaN. Morphological changes of annealed and nitridated samples were analyzed using optical microscopy, scanning electron microscopy, atomic force microscopy. Chemical composition and elemental impurities were analysed by energy dispersive x-ray diffraction. The room-temperature photoluminescence study of annealed samples shows broad emission from 300 nm to 500 nm related to of β-Ga{sub 2}O{sub 3}, whereas nitridated samples show near band edge emission at 370 nm (3.36 eV) which corresponds to GaN.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Plasmonic spectral tunability of conductive ternary nitrides

Conductive binary transition metal nitrides, such as TiN and ZrN, have emerged as a category of promising alternative plasmonic materials. In this work, we show that ternary transition metal nitrides such as Ti{sub x}Ta{sub 1−x}N, Ti{sub x}Zr{sub 1−x}N, Ti{sub x}Al{sub 1−x}N, and Zr{sub x}Ta{sub 1−x}N share the important plasmonic features with their binary counterparts, while having the additional asset of the exceptional spectral tunability in the entire visible (400–700 nm) and UVA (315–400 nm) spectral ranges depending on their net valence electrons. In particular, we demonstrate that such ternary nitrides can exhibit maximum field enhancement factors comparable with gold in the aforementioned broadband range. We also critically evaluate the structural features that affect the quality factor of the plasmon resonance and we provide rules of thumb for the selection and growth of materials for nitride plasmonics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Structure and Hardness of Ceramics Produced through High-Temperature Nitridation of Titanium Foil

We have studied the variation in the phase composition, elemental composition, and microstructure of rolled titanium samples during thermal annealing in a nitrogen atmosphere at 1300, 1500, 1700, and 2000°C. The results demonstrate that the nitridation process can yield compact titanium nitride-based ceramics or TiN/TiN{sub x}/α-Ti〈N〉 heterostructures. X-ray diffraction data for the near-surface region of the samples before and after nitridation and those for cross-sectional fracture surfaces of heterostructures are used to infer orientation relationships between the TiN phase and α-Ti〈N〉 solid solution. Scanning electron microscopy results for cross-sectional fracture surfaces indicate that complete nitridation of the samples leads to the formation of a three-layer microstructure.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Effect of the Sapphire-Nitridation Level and Nucleation-Layer Enrichment with Aluminum on the Structural Properties of AlN Layers

The effect of atomic aluminum deposited onto sapphire substrates with different nitridation levels on the quality of AlN layers grown by ammonia molecular-beam epitaxy is investigated. The nitridation of sapphire with the formation of ~1 monolayer of AlN is shown to ensure the growth of layers with a smoother surface and better crystal quality than in the case of the formation of a nitrided AlN layer with a thickness of ~2 monolayers. It is demonstrated that the change in the duration of exposure of nitrided substrates to the atomic aluminum flux does not significantly affect the parameters of subsequent AlN layers.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ternary Nitride Materials: Fundamentals and Emerging Device Applications

Interest in inorganic ternary nitride materials has grown rapidly over the past few decades, as their diverse chemistries and structures make them appealing for a variety of applications. Due to synthetic challenges posed by the stability of N 2 , the number of predicted nitride compounds dwarfs the number that have been synthesized, offering a breadth of opportunity for exploration. This review summarizes the fundamental properties and structural chemistry of ternary nitrides, leveraging metastability and the impact of nitrogen chemical potential. A discussion of prevalent defects, both detrimental and beneficial, is followed by a survey of synthesis techniques and their interplay with metastability. Throughout the review, we highlight applications (such as solid-state lighting, electrochemical energy storage, and electronic devices) in which ternary nitrides show particular promise.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Compatibility/Stability Issues in the Use of Nitride Kernels in LWR TRISO Fuel

The stability of the SiC layer in the presence of free nitrogen will be dependent upon the operating temperatures and resulting nitrogen pressures whether it is at High Temperature Gas-Cooled Reactor (HTGR) temperatures of 1000-1400°C (coolant design dependent) or LWR temperatures that range from 500-700°C. Although nitrogen released in fissioning will form fission product nitrides, there will remain an overpressure of nitrogen of some magnitude. The nitrogen can be speculated to transport through the inner pyrolytic carbon layer and contact the SiC layer. The SiC layer may be envisioned to fail due to resulting nitridation at the elevated temperatures. However, it is believed that these issues are particularly avoided in the LWR application. Lower temperatures will result in significantly lower nitrogen pressures. Lower temperatures will also substantially reduce nitrogen diffusion rates through the layers and nitriding kinetics. Kinetics calculations were performed using an expression for nitriding silicon. In order to further address these concerns, experiments were run with surrogate fuel particles under simulated operating conditions to determine the resulting phase formation at 700 and 1400°C.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2015

Platinum Nanoparticle Loading of Boron Nitride Aerogel and Its Use as a Novel Material for Low-Power Catalytic Gas Sensing

We report that a high-surface-area, highly crystalline boron nitride aerogel synthesized with nonhazardous reactants has been loaded with crystalline platinum nanoparticles to form a novel nanomaterial that exhibits many advantages for use in a catalytic gas sensing application. The platinum nanoparticle-loaded boron nitride aerogel integrated onto a microheater platform allows for calorimetric propane detection. The boron nitride aerogel exhibits thermal stability up to 900 °C and supports disperse platinum nanoparticles, with no sintering observed after 24 h of high-temperature testing. The high thermal conductivity and low density of the boron nitride aerogel result in an order of magnitude faster response and recovery times (<2 s) than reported on alumina support and allow for 10% duty cycling of the microheater with no loss in sensitivity. Lastly, the resulting 1.5 mW sensor power consumption is two orders of magnitude less than commercially available catalytic gas sensors and unlocks the potential for wireless, battery-powered catalytic gas sensing.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Multipass Scratch Behavior of Borided and Nitrided H13 Steel

AISI H13 steel was subjected to boriding and nitriding; its performance was evaluated by the progressive load scratch test, and then by the multipass scratch test (MPST), to evaluate the accumulated damage. Boriding and nitriding were carried out at a temperature of 800 and 580 °C, respectively, both treatments for 1 and 5 h of exposure time. In scratch test, a load range of 3-90 N was used for borides; a higher range (3-180 N) was chosen for nitrides. Critical loads (L{sub c}) were estimated based on optical microscope observations of the scratch tracks. Failure mechanisms and residual depths were examined by scanning electronic microscope and optical profilometry. Finally, using fractions of L{sub c,} MPST was applied on uncoated and coated samples, for 25, 50, 75 and 100 unidirectional scratch cycles. The coefficient of friction (COF) evolution was recorded and analyzed. A decrease in COF was observed as cycles go through; it was initially higher in uncoated sample; moreover, it was observed that normal load was determinant in its behavior, regardless of the treatment time. Nitrided samples exhibited less catastrophic failures over borided ones, also showed a better volume loss/load ratio performance, from 6 to 8 times better compared to borided samples.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Reactive flash sintering and characterization of bulk high entropy nitrides

Over the past decade, numerous high-entropy ceramics have been synthesized, often displaying attractive properties. However, the study on facile preparation of bulk high entropy nitrides (HEN) are limited, despite its broad potential applications. This research demonstrates for the first time rapid fabrication (within ∼6 min) of bulk high-entropy nitrides, especially (Al 0.17 Nb 0.17 Ta 0.17 Ti 0.32 Zr 0.17 )N, from binary nitride powder mixtures using a highly efficient reactive flash sintering (RFS) technique. X-ray diffraction (XRD) shows the HENs from RFS are near single-phase solid solutions with a rock salt crystal structure, while in situ synchrotron study carried out during RFS captured in real time the formation of HEN, which was preserved upon cooling, suggesting thermodynamic stability of the HEN phase, even up to extreme pressure (∼35.6 GPa). Microscopic analyses using SEM, STEM, and EDS reveal decent uniformity for HEN with no obvious segregation of elements, even to submicron scale. Some properties of the obtained bulk HENs are consistent with expectations. For example, their hardness and bulk modulus are close to estimates based on rule-of-mixture (ROM) values from the constituent binary nitrides. Meanwhile, some other measured properties seem to show surprises. For example, the fracture toughness for the HENs (e.g., 7.81 ± 1.40 MPa•m 1/2 or higher) turns out to be more than double of the expected ROM estimates. The significantly improved fracture toughness is attributed to the observed nano-layered structure of the HENs, despite the HEN’s cubic crystal structure and high hardness. In addition, the oxidation resistance shows improvement up till ∼800°C, possibly due to Ta doping that suppress oxygen vacancy formation in the oxide shell, while the 5-metal HEN of (Al 0.17 Nb 0.17 Ta 0.17 Ti 0.32 Zr 0.17 )N displays superconductivity (T c of ∼5–7 K from magnetism and resistivity measurements, slightly lower than ROM estimate), despite insulating property of starting AlN. Furthermore, future study combining experimental investigation using larger samples to confirm the observed increase in fracture toughness and oxidation resistance, theoretical modeling at different length scale, and more detailed structural/chemical characterization, especially at the atomic scale, are all needed to fully understand the inter-relationships between composition, processing, structure, and novel properties for these HENs and the development of related new materials for different applications.

Flash sintering↗
DOE OSTI2013

The synthesis and structure of new transition metal lithium calcium nitride compounds

Three new nitrides, Li{sub 3}Ca{sub 2}V{sub 0.79}Nb{sub 0.21}N{sub 4}, Li{sub 2}Ca{sub 2.67}Nb{sub 0.33}N{sub 3} and Li{sub 12}Ca{sub 9}W{sub 5}N{sub 20}, were synthesized in sealed niobium tubes using lithium nitride as a flux at temperatures ranging from 800 Degree-Sign C to 1050 Degree-Sign C. In all of these compounds, the transition metals are coordinated tetrahedrally by nitrogen; these tetrahedra are isolated from each other. Bullet Li{sub 3}Ca{sub 2}V{sub 0.79}Nb{sub 0.21}N{sub 4}, space group P2{sub 1}/m (no. 11), cell parameters a=5.7669(8) A, b=6.9123(9) A, c=6.0116(12) A, {beta}=90.727(9) Degree-Sign , Z=2, has a shared vanadium/niobium tetrahedral position which shares vertices with the tetrahedrally-coordinated lithium position. Bullet Li{sub 2}Ca{sub 2.67}Nb{sub 0.33}N{sub 3}, space group Req /o(3, Macron )m (no. 166), cell parameters a=3.6311(2) A, c=29.459(3) A, Z=3, contains a disordered tetrahedral calcium/niobium position, an octahedral calcium position and a triangularly coordinated lithium position. Bullet Li{sub 12}Ca{sub 9}W{sub 5}N{sub 20}, space group C2/c (no. 15), cell parameters a=27.7347(19) A, b=8.6652(6) A, c=10.7685(7) A, {beta}=110.314(2) Degree-Sign , Z=4, contains three crystallographically different tungsten positions as well as one disordered lithium position. - Graphical abstract: Crystal structure of Li{sub 3}Ca{sub 2}V{sub 0.79}Nb{sub 0.21}N{sub 4} depicting the chains of edge-sharing LiN{sub 4} (light hatching) and (V/Nb)N{sub 4} (dark hatching) tetrahedra viewed approximately along the [100] direction. Calcium atoms are shown as open circles and nitrogen atoms are colored black. Highlights: Black-Right-Pointing-Pointer Three new lithium calcium nitrides are synthesized. Black-Right-Pointing-Pointer Lithium nitride flux used in synthesis. Black-Right-Pointing-Pointer Structures contain isolated tetrahedrally coordinated transition metals. Black-Right-Pointing-Pointer Li{sub 12}Ca{sub 9}W{sub 5}N{sub 20} contains three crystallographically different W positions.

36 MATERIALS SCIENCE↗
DOE OSTI2014

2D to 3D transition of polymeric carbon nitride nanosheets

The transition from a prevalent turbostratic arrangement with low planar interactions (2D) to an array of polymeric carbon nitride nanosheets with stronger interplanar interactions (3D), occurring for samples treated above 650 °C, was detected by terahertz-time domain spectroscopy (THz-TDS). The simulated 3D material made of stacks of shifted quasi planar sheets composed of zigzagged polymer ribbons, delivered a XRD simulated pattern in relatively good agreement with the experimental one. The 2D to 3D transition was also supported by the simulation of THz-TDS spectra obtained from quantum chemistry calculations, in which the same broad bands around 2 THz and 1.5 THz were found for 2D and 3D arrays, respectively. This transition was also in accordance with the tightening of the interplanar distance probably due to an interplanar π bond contribution, as evidenced also by a broad absorption around 2.6 eV in the UV–vis spectrum, which appeared in the sample treated at 650 °C, and increased in the sample treated at 700 °C. The band gap was calculated for 1D and 2D cases. The value of 3.374 eV for the 2D case is, within the model accuracy and precision, in a relative good agreement with the value of 3.055 eV obtained from the experimental results. - Graphical abstract: 2D lattice mode vibrations and structural changes correlated with the so called “2D to 3D transition”. - Highlights: • A 2D to 3D transition has been detected for polymeric carbon nitride. • THz-TDS allowed us to discover and detect the 2D to 3D transition of polymeric carbon nitride. • We propose a structure for polymeric carbon nitride confirming it with THz-TDS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

A new method for isolating plasma interactions from those of the laser beam during plasma nitriding

Highlights: • Nitriding of titanium was studied using a laser sustained plasma (LSP) reactor, independent of the laser beam. • Nucleation and growth of faceted, dendritic, rectangular and particulate TiN morphologies was observed. • TiN layers up to 300 μm thick formed within 5 s - one of the most rapid TiN growth rates observed for LSP/laser nitriding. • LSP accessed novel microstructures compared to laser nitriding with or without surface-struck plasm plasma. - Abstract: A new method for separating the interactions of a laser plasma from those of a laser beam with a titanium substrate was developed. A laser-sustained plasma (LSP) was generated by striking the plasma on a titanium plate in a flowing nitrogen atmosphere at ambient pressure and subsequently removing the strike plate. The resultant nitrogen plasma was sustained indefinitely around the laser focal plane until the nitrogen gas flow and/or the laser power were switched off. The laser-sustained nitrogen plasma was then used as a “reactor” to study the effects of a nitrogen plasma, independent of the laser beam, when the plasma was brought into close proximity, (2 to 3 mm), parallel to a titanium substrate. There was no interaction of the parallel laser beam with the substrate. Heat, nitrogen and titanium were exchanged between the nitrogen LSP and substrate resulting in melting, nucleation and growth of faceted and dendritic TiN crystals, rectangular hollow TiN morphologies and particulate TiN deposits. Dense TiN layers up to 300 μm thick formed within 5 s. The results demonstrated that compositionally graded layers of nitrogen-enriched titanium, and titanium nitride could be formed very rapidly on model, commercially-pure titanium substrates, with promise for extension to commercial alloys such as Ti-6Al-4V.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Facile synthesis of phosphorus doped graphitic carbon nitride polymers with enhanced visible-light photocatalytic activity

Graphical abstract: - Highlights: • P-doped g-C{sub 3}N{sub 4} has been prepared by a one-pot green synthetic approach. • The incorporation of P resulted in favorable textural and electronic properties. • Doping with P enhanced the visible-light photocatalytic activity of g-C{sub 3}N{sub 4}. • A postannealing treatment further enhanced the activity of P-doped g-C{sub 3}N{sub 4}. • Photogenerated holes were the main species responsible for the activity. - Abstract: Phosphorus-doped carbon nitride materials were prepared by a one-pot green synthetic approach using dicyandiamide monomer and a phosphorus containing ionic liquid as precursors. The as-prepared materials were subjected to several characterizations and investigated as metal-free photocatalysts for the degradation of organic pollutants (dyes like Rhodamine B, Methyl orange) in aqueous solution under visible light. Results revealed that phosphorus-doped carbon nitride have a higher photocatalytic activity for decomposing Rhodamine B and Methyl orange in aqueous solution than undoped g-C{sub 3}N{sub 4}, which was attributed to the favorable textural, optical and electronic properties caused by doping with phosphorus heteroatoms into carbon nitride host. A facile postannealing treatment further improved the activity of the photocatalytic system, due to the higher surface area and smaller structural size in the postcalcined catalysts. The phosphorus-doped carbon nitride showed high visible-light photocatalytic activity, making them promising materials for a wide range of potential applications in photochemistry.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Phosphides or nitrides for better NLO properties? A detailed comparative study of alkali metal doped nano-cages

Highlights: • Alkali metal doped boron and aluminum phosphide nano-cages are evaluated for NLO properties. • The NLO response of phosphide nano-cages is compared with nitride nano-cages. • Phosphide nano-cages show better NLO properties than the corresponding nitride nano-cages. • Conductivity of doped nano-cages is much higher than pristine nano-cages. • MAl{sub 11}P{sub 12} and MB{sub 11}P{sub 12} show monotonic increase in hyperpolarizability with size of alkali metal. - Abstract: Phosphide nano-cages of MX{sub 12}P{sub 11} and MX{sub 11}P{sub 12} (where X = B or Al, M = Li, Na, K) are investigated theoretically for geometric, electronic and nonlinear optical (NLO) properties. Alkali metal is doped by replacing (a) aluminum or boron atom and (b) phosphorus atom. Alkali metal doping can remarkably alter the electronic and NLO properties of the nano-cages, regardless of doping site. HOMO-LUMO gap is decreased whereas first hyperpolarizability is enhanced significantly in doped AlP and BP nano-cages. PDOS (partial density of states) analysis suggests that diffuse excess electrons from alkali metal play important role in boosting NLO properties of phosphide nano-cages. TD-DFT calculations are performed to study the effect of alkali metal doping on absorption spectra. Red shift is observed in the UV–vis spectra of all considered nano-cages. Comparison of phosphide nano-cages with nitride nano-cages indicated that doping nitride nano-cages with alkali metal leads to greater hyperpolarizability and NLO response than doping phosphide nano-cages.

36 MATERIALS SCIENCE↗
DOE OSTI2022

CeTaN 3 and CeNbN 3 : Prospective Nitride Perovskites with Optimal Photovoltaic Band Gaps

Perovskites constitute an exceptionally tunable materials family with diverse applications in electronics, optoelectronics, energy, and quantum technologies. Out of the thousands of known perovskites, the majority of compounds are oxides, halides, and chalcogenides. In contrast, only two nitride perovskites are currently known. In this work we perform a thorough ab initio computational screening of possible nitride perovskites, and we identify two new compounds, CeNbN 3 and CeTaN 3 , with band gaps in the near-infrared to visible range, depending on temperature. In their room-temperature orthorhombic phase, we predict that both compounds exhibit direct or quasidirect band gaps in the range 1.1–2.0 eV, with the Pnma phases matching the Shockley–Queisser limit for photovoltaic energy conversion efficiency. Further, these compounds are also predicted to be strong light absorbers, with absorption coefficients surpassing those of high-performance semiconductors such as GaAs and CH 3 NH 3 PbI 3 . The present findings reveal a potentially new class of nitride semiconductors with promise for electronics, optoelectronics, and light harvesting and for integration with existing nitride-based lighting technology.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Unraveling In-Situ Formation of Surface Nickel Nitride Structures in Plasma-Assisted Catalytic Ammonia Synthesis

We report the in situ formation of Ni nitride for plasma-assisted ammonia synthesis. Both the surface nitrogen concentration and the ammonia formation rate exhibit dependence on the N 2 :H 2 feed ratio. The maximum surface nitrogen concentration occurs at a N 2 :H 2 ratio of 4:1, and the maximum catalytic activity occurs at 2:1. In contrast, the formation of gas phase radicals is less sensitive to feed composition, indicating that Ni nitride is more kinetically relevant to ammonia production than gas-phase radicals. The plasma-induced formation of Ni nitride is therefore proposed to be a critical contributor to the synergistic effects in plasma-assisted catalytic ammonia synthesis. Additionally, Ni nitride alters the surface reaction mechanism of plasma-assisted ammonia synthesis, with the rate-determining-step (RDS) shifting to surface-bound NH 3 formation rather than N 2 activation at temperatures below 373 K. These findings provide mechanistic insight that opens opportunities for optimizing the performance of plasma-assisted catalytic ammonia synthesis

Ammonia↗
DOE OSTI2017

Nanoporous Boron Nitride as Exceptionally Thermally Stable Adsorbent: Role in Efficient Separation of Light Hydrocarbons

Here in this work, nanoporous boron nitride sample was synthesized with a Brunauer–Emmett–Teller (BET) surface area of 1360 m 2 /g and particle size 5–7 μm. The boron nitride was characterized with X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electron microscopy (TEM and SEM). Thermogravimetric analysis (TGA) under nitrogen and air and subsequent analysis with XPS and XRD suggested that its structure is stable in air up to 800 °C and in nitrogen up to 1050 °C, which is higher than most of the common adsorbents reported so far. Nitrogen and hydrocarbon adsorption at 298 K and pressure up to 1 bar suggested that all hydrocarbon adsorption amounts were higher than that of nitrogen and the adsorbed amount of hydrocarbon increases with an increase in its molecular weight. The kinetics of adsorption data suggested that adsorption becomes slower with the increase in molecular weight of hydrocarbons. The equilibrium data suggested that that boron nitride is selective to paraffins in a paraffin–olefin mixture and hence may act as an “olefin generator”. The ideal adsorbed solution theory (IAST)-based selectivity for CH 4 /N 2 , C 2 H 6 /CH 4 , and C 3 H 8 /C 3 H 6 was very high and probably higher than the majority of adsorbents reported in the literature. IAST-based calculations were also employed to simulate the binary mixture adsorption data for the gas pairs of CH 4 /N 2 , C 2 H 6 /CH 4 , C 2 H 6 /C 2 H 4 , and C 3 H 8 /C 3 H 6 . Lastly, a simple mathematical model was employed to simulate the breakthrough behavior of the above-mentioned four gas pairs in a dynamic column experiment. The overall results suggest that nanoporous boron nitride can be used as a potential adsorbent for light hydrocarbon separation.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Ammonia Synthesis by a Supported Iron-Lithium Hydride Precatalyst: Silicon Nitride Support Enabled Synthesis and Nitrogen Reservoir Dynamics

Amorphous silicon nitride (Si 3 N 4 ) is an unconventional support for the chemisorption of organometallic complexes and offers potential improvements in active site stability and reactivity through enhanced metal-nitrogen covalency and orbital overlap in bonding interactions with the nitride framework. Here, we show that silicon nitride-supported iron mesityl complexes display divergent reactivity compared to their silica-supported homologues, resisting metallic particle formation under reducing pretreatment conditions (exposure to excess organolithium reagents) and maintaining active iron/lithium speciation under ammonia synthesis conditions that is absent on the oxide support. When the organometallic iron complex on silicon nitride is exposed to excess n-butyllithium, iron remains isolated, catalyzing the conversion of butyllithium to lithium hydride, resulting in a divalent iron site in a polyhydride environment. In contrast, the silica-supported complex is converted to reduced iron clusters without forming persistent isolated hydrides. These structural differences lead to markedly different catalytic behaviors under ammonia synthesis conditions. The Li/Fe/Si 3 N 4 catalyst is highly active (7.5 mol NH 3 /mol Fe/h at 300 °C, 10 bar, or 46 mol NH 3 /mol Fe/h at 400 °C, 10 bar), while both the silica-supported analog and the nonlithiated Si 3 N 4 -supported species are inactive. Notably, this activity is enhanced relative to previously reported iron-lithium hydride composite catalysts (0.43–4.1 mol NH 3 /mol Fe/h at 300 °C, 10 bar) and relative to the industrial benchmark promoted iron catalyst KM1 (3.0 mol NH 3 /mol Fe/h at 400 °C, 10 bar). The catalyst activation and LiH/LiNH x nitrogen reservoir dynamics for Li/Fe/Si 3 N 4 are studied by X-ray Absorption, Mössbauer, and in situ DRIFT spectroscopies and isotopic exchange kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗