13767-16-3

Usage

Uses

Labelled Ammonia.

InChI:InChI=1/H3N/h1H3/i1+1

Upstream product

• 7727-37-9 nitrogen 
• 1333-74-0 hydrogen 
• 2067-80-3 urea-15N₂ 
• 80937-33-3 oxygen 
• 10102-44-0 Nitrogen dioxide 
• 29817-79-6 nitrogen-15 
• 7783-06-4 hydrogen sulfide 
• 39466-62-1 [⁽¹⁵⁾N]ammonium chloride 
• 1310-73-2 sodium hydroxide 
• 29817-79-6 [¹⁵N₂]-hydrazine 
• 7664-41-7 ammonia 
• 15917-77-8 ¹⁵N labeled nitric oxide 
• 72960-76-0 ¹⁵N-hydroxylamine 
• 7664-93-9 sulfuric acid 

Downstream Products

• 22364-56-3 ammonia-⁽¹⁵⁾N-d3 
• 144495-71-6 Pt(Se₂⁽¹⁵⁾N₂)(P(CH₃)2C₆H₅)2 
• 14390-96-6 ⁽¹⁵⁾N⁽¹⁾H₂ 
• 1427772-51-7 [Fe(¹⁵N_H3)H(Et₂PCH₂N(Me)CH₂PEt₂)(dmpm)]B(C₆F₅)₄ 
• 144541-60-6 {Pt(⁽¹⁵⁾NSO)2(P(CH₃)2(C₆H₅))2} 

Relevant academic research and scientific papers

Catalytic Hydrogenation of a Manganese(V) Nitride to Ammonia

The catalytic hydrogenation of a metal nitride to produce free ammonia using a rhodium hydride catalyst that promotes H2 activation and hydrogen-atom transfer is described. The phenylimine-substituted rhodium complex (η5-C5Me5)Rh(MePhI)H (MePhI = N-methyl-1-phenylethan-1-imine) exhibited higher thermal stability compared to the previously reported (η5-C5Me5)Rh(ppy)H (ppy = 2-phenylpyridine). DFT calculations established that the two rhodium complexes have comparable Rh-H bond dissociation free energies of 51.8 kcal mol-1 for (η5-C5Me5)Rh(MePhI)H and 51.1 kcal mol-1 for (η5-C5Me5)Rh(ppy)H. In the presence of 10 mol% of the phenylimine rhodium precatalyst and 4 atm of H2 in THF, the manganese nitride (tBuSalen)MnN underwent hydrogenation to liberate free ammonia with up to 6 total turnovers of NH3 or 18 turnovers of H? transfer. The phenylpyridine analogue proved inactive for ammonia synthesis under identical conditions owing to competing deleterious hydride transfer chemistry. Subsequent studies showed that the use of a non-polar solvent such as benzene suppressed formation of the cationic rhodium product resulting from the hydride transfer and enabled catalytic ammonia synthesis by proton-coupled electron transfer.

Single-atom molybdenum immobilized on photoactive carbon nitride as efficient photocatalysts for ambient nitrogen fixation in pure water

A series of Mo single-atom catalysts were prepared by calcining a low-cost primary material of urea with various amounts of Na2MoO4·2H2O. Isolated Mo centers are immobilized on in situ formed polymeric carbon nitride via coordinating with two N donors to form two-coordinated MoN2 species. The low-coordinated Mo centers can serve as active sites for N2 chemisorption and activation, achieving high photocatalytic activity for NH3 evolution with a rate of 50.9 μmol gcat-1 h-1 in pure water. In the presence of ethanol as the electron scavenger, the NH3 evolution rate can reach 830 μmol gcat-1 h-1, and the catalyst shows a quantum efficiency of 0.70% at 400 nm. This is the first single-atom catalyst that can drive photocatalytic N2 fixation in pure water with comparable performance to recent reports for photocatalytic N2 reduction. Experimental investigations and density functional theory calculations demonstrate that the coordinatively unsaturated metal center in the single-atom catalysts can strongly adsorb N2via an end-on configuration to elongate the NN bond from 1.11 ? to 1.15 ?, and thus photoexcited electrons can transfer to the weakened NN bond for efficient nitrogen fixation under ambient conditions. These findings provide new insight for solar-driven N2 fixation by atomically dispersing low-coordination metal centers on photoactive supports.

Direct Electrochemical Ammonia Synthesis from Nitric Oxide

NO removal from exhausted gas is necessary owing to its damage to environment. Meanwhile, the electrochemical ammonia synthesis (EAS) from N2 suffers from low reaction rate and Faradaic efficiency (FE). Now, an alternative route for ammonia synthesis is proposed from exhaust NO via electrocatalysis. DFT calculations indicate electrochemical NO reduction (NORR) is more active than N2 reduction (NRR). Via a descriptor-based approach, Cu was screened out to be the most active transition metal catalyst for NORR to NH3 owing to its moderate reactivity. Kinetic barrier calculations reveal NH3 is the most preferred product relative to H2, N2O, and N2 on Cu. Experimentally, a record-high EAS rate of 517.1 μmol cm?2 h?1 and FE of 93.5 percent were achieved at ?0.9 V vs. RHE using a Cu foam electrode, exhibiting stable electrocatalytic performances with a 100 h run. This work provides an alternative strategy to EAS from exhaust NO, coupled with NO removal.

Metal-free Transformations of Nitrogen-Oxyanions to Ammonia via Oxoammonium Salt

Transformations of nitrogen-oxyanions (NOx?) to ammonia impart pivotal roles in sustainable biogeochemical processes. While metal-mediated reductions of NOx? are relatively well known, this report illustrates proton-assisted transformations of NOx? anions in the presence of electron-rich aromatics such as 1,3,5-trimethoxybenzene (TMB?H, 1 a) leading to the formation of diaryl oxoammonium salt [(TMB)2N+=O][NO3?] (2 a) via the intermediacy of nitrosonium cation (NO+). Detailed characterizations including UV/Vis, multinuclear NMR, FT-IR, HRMS, X-ray analyses on a set of closely related metastable diaryl oxoammonium [Ar2N+=O] species disclose unambiguous structural and spectroscopic signatures. Oxoammonium salt 2 a exhibits 2 e? oxidative reactivity in the presence of oxidizable substrates such as benzylamine, thiol, and ferrocene. Intriguingly, reaction of 2 a with water affords ammonia. Perhaps of broader significance, this work reveals a new metal-free route germane to the conversion of NOx to NH3.

Self-organized Ruthenium–Barium Core–Shell Nanoparticles on a Mesoporous Calcium Amide Matrix for Efficient Low-Temperature Ammonia Synthesis

A low-temperature ammonia synthesis process is required for on-site synthesis. Barium-doped calcium amide (Ba-Ca(NH2)2) enhances the efficacy of ammonia synthesis mediated by Ru and Co by 2 orders of magnitude more than that of a conventional Ru catalyst at temperatures below 300 °C. Furthermore, the presented catalysts are superior to the wüstite-based Fe catalyst, which is known as a highly active industrial catalyst at low temperatures and pressures. Nanosized Ru–Ba core–shell structures are self-organized on the Ba-Ca(NH2)2 support during H2 pretreatment, and the support material is simultaneously converted into a mesoporous structure with a high surface area (>100 m2 g?1). These self-organized nanostructures account for the high catalytic performance in low-temperature ammonia synthesis.

Generating Defect-Rich Bismuth for Enhancing the Rate of Nitrogen Electroreduction to Ammonia

The electrochemical N2 fixation, which is far from practical application in aqueous solution under ambient conditions, is extremely challenging and requires a rational design of electrocatalytic centers. We observed that bismuth (Bi) might be a promising candidate for this task because of its weak binding with H adatoms, which increases the selectivity and production rate. Furthermore, we successfully synthesized defect-rich Bi nanoplates as an efficient noble-metal-free N2 reduction electrocatalyst via a low-temperature plasma bombardment approach. When exclusively using 1H NMR measurements with N2 gas as a quantitative testing method, the defect-rich Bi(110) nanoplates achieved a 15NH3 production rate of 5.453 μg mgBi?1 h?1 and a Faradaic efficiency of 11.68 % at ?0.6 V vs. RHE in aqueous solution at ambient conditions.

Single-atom metal-N4site molecular electrocatalysts for ambient nitrogen reduction

Electrochemical N2reduction to NH3is an emerging energy technology, attracting much attention due to its features of mild reaction conditions and being non-polluting. In this work, we demonstrate that a well-defined cobalt tetraphenylporphyrin (CoTPP) molecule as a model catalyst exhibits good electrocatalytic nitrogen reduction activity in 0.1 M HCl electrolyte with an ammonia yield of 15.18 ± 0.78 μg h-1mg-1cat.calculated by the indophenol blue method and a Faraday efficiency (FE) of 11.43 ± 0.74%. The catalyst also has satisfactory electrolytic stability and recycling test reusability. The activity displayed by the porphyrin molecular catalysts is attributed to the full exposure of the metal-N4sites. To trace the source of ammonia, an isotope labeling experiment (15N2as the feed gas) is used to calculate the ammonia yieldvia1H nuclear magnetic resonance (NMR), which is close to that of the indophenol blue method. In addition, we replace the central metal to prepare CuTPP and MnTPP, and they also show electrocatalytic nitrogen reduction reaction (NRR) ability. This work proves the feasibility and versatility of using metalloporphyrin molecules as model electrocatalysts for NRR and offers a new strategy for the further development of molecular NRR catalysts.

A highly active defect engineered Cl-doped carbon catalyst for the N2reduction reaction

eNRR is a promisingly environment-friendly strategy to obtain ammonia under ambient conditions. For metal-based catalysts, the competitive adsorption of H+over N2remains the primary hurdle for high ammonia yield and faradaic efficiency. Carbon-based metal-free catalysts attract our attention for the potential of being promising NRR catalysts due to their natural low HER activity. In this study, we prepared a modified Zn-based metal-organic framework (Zn-BTC) decorated with Cl ions by simply adding NaCl in the synthetic process. The existence of Cl ions in the framework contributes to the generation of large pores during thermolysis. Moreover, -Cl and -COCl species were formedin situand connected with carbon atoms in the defect area. Benefitting from such a structure, this catalyst achieves a high ammonia yield rate of 103.96 μg h?1mgcat?1and a faradaic efficiency of 21.71% at room temperature. Theoretical results also proved that the newly produced -COCl and -Cl functional groups could attract more electrons from adjacent carbon atoms due to their stronger electronegativity, thus improving its affinity towards N2while lowering the HER activity as reactive sites.

Schottky Barrier-Induced Surface Electric Field Boosts Universal Reduction of NOx? in Water to Ammonia

NOx? reduction acts a pivotal part in sustaining globally balanced nitrogen cycle and restoring ecological environment, ammonia (NH3) is an excellent energy carrier and the most valuable product among all the products of NOx? reduction reaction, the selectivity of which is far from satisfaction due to the intrinsic complexity of multiple-electron NOx?-to-NH3 process. Here, we utilize the Schottky barrier-induced surface electric field, by the construction of high density of electron-deficient Ni nanoparticles inside nitrogen-rich carbons, to facilitate the enrichment and fixation of all NOx? anions on the electrode surface, including NO3? and NO2?, and thus ensure the final selectivity to NH3. Both theoretical and experimental results demonstrate that NOx? anions were continuously captured by the electrode with largely enhanced surface electric field, providing excellent Faradaic efficiency of 99 % from both electrocatalytic NO3? and NO2? reduction. Remarkably, the NH3 yield rate could reach the maximum of 25.1 mg h?1 cm?2 in electrocatalytic NO2? reduction reaction, outperforming the maximum in the literature by a factor of 6.3 in neutral solution. With the universality of our electrocatalyst, all sorts of available electrolytes containing NOx? pollutants, including seawater or wastewater, could be directly used for ammonia production in potential through sustainable electrochemical technology.

Reactions of Water and Ammonia with Bis(pentamethylcyclopentadienyl) Complexes of Zirconium and Hafnium

The propensity for the group 4B metal center to form extremely strong bonds with oxygen and nitrogen donors is often invoked as an important driving force in the reductions of carbon monoxide and dinitrogen with organometallic derivatives of these metals, e.g., Cp*2MLx (Cp*=η5-C5Me5; M=Ti, Zr, Hf).In order to assess some of the fundamental bonding properties of hydroxide, oxo, and amide ligands with bis(pentamethylcyclopentadienyl) derivatives of zirconium and hafnium, the reactivities of water and ammonia with several Cp*2MLx (M=Zr, Hf) complexes have been examined.Water reacts in a clean, stepwise manner with Cp*2MH2 (M=Zr, Hf) to afford Cp*2M(H)(OH), (Cp*2MH)2O, Cp*2M(OH)2, and finally Cp*2M(OH)2*H2O.Cp*2M(H)(Cl) yields Cp*2M(OH)(Cl).Cp*2MH2 reacts with Cp*2M(OH)(X) (X=Cl, OH, H) to afford Cp*2(X)M-O-M(H)Cp*2.In all cases, conversion of a M-H bond to an M-O bond is accompanied by H2 evolution.Similarly, ammonia reacts rapidly with Cp*2MH2 to yield Cp*2M(H)(NH2) and H2.Excess ammonia or Cp*2MH2 do not react further, although exchange with free (15)NH3 is observed.Cp*2Hf(H)(NH2) reacts with H2O to afford Cp*2Hf(H)(OH) and NH3, but not Cp*2Hf(OH)(NH2).Free water undergoes rapid proton exchange and slower oxygen exchange with the hydroxo derivatives. (Cp*2ZrN2) N2 reacts rapidly and cleanly with an equivalent of water to produce N2 (3 equiv) and (Cp*2ZrH)2O.Evidence in support of a stepwise oxidative addition of both O-H bonds via the intermediacy of Cp*2Zr(H)(OH) is presented. 1H and 17O NMR spectra of these new compounds are also tabulated.