Low Activation Energy Pathway for the Catalyzed Reduction of Nitrogen Oxides to N<Subscript>2</Subscript> by Ammonia

A low activation energy pathway for the catalytic reduction of nitrogen oxides to N₂, with reductants other than ammonia, consists of two sets of reaction steps. In the first set, part of the NO _x is reduced to NH₃; in the second set ammonium nitrite, NH₄NO₂ is formed from this NH₃ and NO + NO₂. The NH₄NO₂ thus formed decomposes at ~100 °C to N₂ + H₂O, even on an inert support, whereas ammonium nitrate, NH₄NO₃, which is also formed from NH₃ and NO₂ + O₂, (or HNO₃), decomposes only at 312 °C yielding mainly N₂O. Upon applying Redhead's equations for a first order desorption to the decomposition of ammonium nitrite, an activation energiy of 22.4 is calculated which is consistent with literature data. For the reaction path via ammonium nitrite a consumption ratio of 1/1 for NO and NO₂ is predicted and confirmed experimentally by injecting NO into a mixture of NH₃ + NO₂ flowing over a BaNa/Y catalyst. This leads to a yield increase of one N₂ molecule per added molecule of NO. Little N₂ is produced from NH₃ + NO in the absence of NO₂.     

Spectroscopic Evidence for a Nitrite Intermediate in the Catalytic Reduction of NOx with Ammonia on Fe/MFI

The mechanism of selective catalytic reduction (SCR) of NO_x with NH₃ over Fe/MFI was studied using in situ FTIR spectroscopy. Exposing Fe/MFI first to NH₃ then to flowing NO + O₂ or using the reversed sequence, invariably leads to the formation of ammonium nitrite, NH₄NO₂. In situ FTIR results in flowing NO + NH₃ + O₂ at different temperatures show that NH₃ is strongly adsorbed and reacts with impinging NO_x. The intensity of the NH₄NO₂ bands initially increases with temperature, but passes through a maximum at 120 °C because the nitrite decomposes to N₂ + H₂O. The mechanistic model rationalizes that the consumption ratio of NO and NH₃ is close to unity and that the effect of water vapor depends on the reaction temperature. At high temperature H_2O enhances the rate because it is needed to form NH₄NO₂. At low temperature, when adsorbed H₂O is abundant it lowers the rate because it competes with NO_x for adsorption sites.     

Modeling the Reactions Between Ammonia and Dinitrogen Pentoxide to Synthesize Ammonium Dinitramide (ADN)

Only three references about the reactions of ammonia (NH₃) with dinitrogen pentoxide (N₂O₅) have been published in the course of the last 150 years. None of them describes the reactions referring to the products in dependence on the reaction conditions. In this report the experimental results due to the reaction of NH₃ and N₂O₅ lead to three equations. One of these, the formation of dinitrogen oxide (N₂O) in addition to ammonium nitrate (NH₄NO₃; AN) was not mentioned before in the references available. The other reactions are known as the formation of ammonium dinitramide (NH₄N(NO₂)₂; ADN) and AN beside the formation and decomposition of nitramide (NH₂NO₂; NA) into water and dinitrogen oxide. Summarizing the known reactions of NH₃ with N₂O₅ and those of the intermediate products in a reaction scheme a model was established for the selectivity of ammonium dinitramide (ADN) and for the dependence on the reaction conditions. The model is in good accordance with the experimental results.     

NO reduction with H2 in the presence of excess O2 over Pd/MFI catalyst

The NO SCR (selective catalytic reduction) activity with H₂ in the presence of excess O₂ was investigated over Pd/MFI catalyst prepared by sublimation method. With GHSV=90?000 h⁻¹, a very high steady-state conversion of NO to N₂ (70%) is achieved at 100 °C. Significant reorganizations take place inside the catalyst upon its first contact with all reactants and products at the reaction temperature. Pd⁰, which has a significant role in the NO-H₂-O₂ reaction, is possibly the active site for NO reduction. The formation of Pd-β hydride deactivates the catalyst for NO reduction. Throughout the entire NO-H₂-O₂ reaction, no N₂O or NO₂ is formed; N₂ is the only N-containing product. The presence of O₂ inhibits the formation of undesirable NH₃. The rate of the NO+H₂ reaction is fast or comparable to that of the H₂+O₂ reaction. The oxidation of Pd⁰ and subsequent agglomeration of PdO are responsible for the decreased NO reduction activity at high temperature.     

Influences of pH on the structure,morphology and dielectric properties of bismuth titanate ceramics produced by a low-temperature self-combustion synthesis without an additional fuel agent

Bismuth titanate (BIT) ceramics were prepared by incorporating low-temperature self-combustion synthesis and pH modification. The pH value of the initial precursor was adjusted to 3, 5 and 7 by the addition of ammonium hydroxide (NH₄OH) with different amount. The reaction between ammonium ions (NH₄⁺) and nitrate ions (NO₃^?) induced the formation of ammonium nitrate (NH₄NO₃), in turn to favor the combustion by enhancing the decomposition rate. Excessive hydroxyl ions (OH^?) at higher pH value dominated the chelating of the metal carboxylate and the metal ions, resulting in a strong hybridization between bismuth (Bi) and oxygen (O), and also the suppression of the independent volatility of Bi and bismuth oxide (Bi₂O₃). Such conditions contributed to the formation of pure BIT via the low-temperature self-combustion synthesis without the use of an additional fuel agent. A BIT ceramic with high relative density (91.35%) that exhibited a high dielectric constant of ～340 and a low dissipation factor ～0.028 was obtained by the synthesis method at the neutral condition. Furthermore, it offers ability for the use in high temperature applications up to 675 °C.     

Direct electron-transfer and electrochemical catalysis of hemoglobin immobilized on mesoporous Al2O3

The direct electrochemistry of hemoglobin (Hb) has been achieved by immobilizing Hb on mesoporous Al₂O₃ (meso-Al₂O₃) film modified glassy carbon (GC) electrode. Meso-Al₂O₃ shows significant promotion to the direct electron-transfer of Hb, thus it exhibits a pair of well defined and quasi-reversible peaks with a formal potential of −0.345 V (vs. SCE). The electron-transfer rate constant (k_s) is estimated to be 3.17 s⁻¹. The immobilized Hb retains its biological activity well and shows high catalytic activity to the reduction of hydrogen peroxide (H₂O₂) and nitrite (NO₂⁻). Under the optimized experimental conditions, the catalytic currents are linear to the concentrations of H₂O₂ and NO₂⁻ in the ranges of 0.195-20.5 μM and 0.2-10 mM, respectively. The corresponding detection limits are 1.95 × 10⁻⁸ M and 3 × 10⁻⁵ M (S/N = 3). The resulting protein electrode has high thermal stability and good reproducibility due to the protection effect of meso-Al₂O₃. Ultraviolet visible (UV-vis) absorption spectra and reflection-absorption infrared (RAIR) spectra display that Hb keeps almost natural structure in the meso-Al₂O₃ film. The N₂ adsorption-desorption experiments show that the pore size of meso-Al₂O₃ is about 14.4 nm, suiting for the encapsulation of Hb (average size: 5.5 nm) well. Therefore, meso-Al₂O₃ is an alternative matrix for protein immobilization and biosensor preparation.     

An acid catalyzed step in the catalytic reduction of NO x to N2

Contact of adsorbed ammonium nitrite, NH₄NO₂, with HCl vapor or a solid acid such as the zeolite HY, significantly lowers the temperature of its decomposition to N₂ + H₂O. Protonated NH₄NO₂ decomposes at room temperature. The decomposition of ammonium nitrite is one of the steps in the catalytic reduction of NO _x with ammonia or other reductants.     

New approaches to prepare nitrogen-doped TiO2 photocatalysts and study on their photocatalytic activities in visible light

Nitrogen-doped TiO₂ nanocatalysts were successfully synthesized by adjusting a pH range using the ammonium nitrate and ammonia water as the nitrogen source. The samples were characterized by XRD, XPS and UV-DRS. When the total amount of ammonium nitrate and ammonia water was unchanged, different pH values were modified by changing the NH₄NO₃/NH₃·H₂O ratio to prepare nitrogen-doped TiO₂. The prepared photocatalyst showed the highest photo-activity for the degradation of 2,4-dichlorophenol (2,4-DCP) under visible light when prepared at pH 5.87. XPS analysis showed the presence of nitrogen in two states doped in TiO₂. The results indicated the photocatalytic activity of N-TiO₂ is varied with the change of pH values, the amount of the nitrogen sources and water. The experimental results showed that the higher activity is due to the variation in the concentration and states of nitrogen-doped in TiO₂. In the preparation methods, the photocatalyst was treated with the hydrogen peroxide before calcination, resulting in the decrease of nitrogen doped into the lattice and the photo-degradation rate of 2,4-DCP. The results suggested that the nitrogen source could be doped into the crystal lattice only in the form of reduction state as NH₄⁺ ion during the calcination process.     

Effect of gas-liquid phase compositions on NO2 and NO absorption into ammonium-sulfite and bisulfite solutions

The effect of gas-liquid phase compositions on NO and NO₂ absorption into ammonium-sulfite and bisulfite solutions is investigated. Preliminary experiment results indicate that the concentrations of (NH₄)₂SO₃ or NH₄HSO₃ solution and the molar ratio for HSO₃⁻ to the total solution concentrations all have significant impact on NO₂ and NO absorption rates. While the solution concentration is constant, the absorption of NO_x mixture is strongly related to the ratio NO₂/NO_x. The absorption rate of NO is primarily affected by NO₂ inlet concentration, and the NO absorption rate reaches the maximum value in (NH₄)₂SO₃ solution with the increase of NO₂ inlet concentration, which is determined by the reaction of NO and NO₂ with SO₃²⁻ as well as NO formation. Moreover, when the solution is NH₄HSO₃ the best ratio of NO₂/NO for the maximum value of the NO absorption rate becomes less or smaller. Meanwhile, the presence of NO in the gas phase is also favorable to the absorption rate of NO₂ in ammonium-sulfite or bisulfite solutions. The total results suggest that the coexistence of NO and NO₂ in the flue gas could enhance the absorption of each other to some extent.     

ION EXCHANGE PROPERTIES OF BiO(NO3) 0.5H2O TOWARDS FLUORIDE IONS

ABSTRACT

We studied the ion exchange behavior of the inorganic anion exchanger BiO(NO₃)0.5H₂O with regard to fluoride ions. The ion exchange reaction was rapid at pH 1, 6.6, and 12. The mechanisms of ion exchange reactions at pH 1 and pH 2-12 were studied in a solution with fluoride ions excess to BiO(NO₃)0.5H₂O. A mixture of the β-phase and an unknown phase was produced in the solution at pH 1. BiOF was produced at pH 2-12. Fluoride ions did not react at pH 13, due to the decomposition of BiO(NO₃) 0.5H₂O at pH 13 to yield Bi₂O₃ (major) and Bi₂O₂CO₃ (minor). The structure of the reaction products depended on the solution pH, mole ratios of BiO(NO₃)0.5H₂O to F’, and the reaction time. We observed that BiO(NO₃)0.5H₂O is capable of removing 99% of the fluoride ions from the solution at pH 1-12 under optimal conditions. The ion exchange reaction of BiO(NO₃)0.5H₂O with fluoride ions was studied under the co-existence of both Cl and Br^?at pH 1, 6.6, 12, and 13. The order of decreasing affinity was found to be (Br^?, Cl^?)> F^?. The reaction product was not a simple mixture of BiOCl, BiOBr, and bismuth oxide fluorides, but an unknown compound.     

A novel approach to non-segmented flow analysis: Part 3. Nitrate,nitrite and ammonium in waters

A high-performance continuous-flow analyser is used for the analysis of nitrate, nitrite and ammonium ion in potable waters. The results demonstrate that (1) the analyser allows the sequential determination of a number of analytes without requiring modification to the manifold; (2) the use of programmed slicing of the reaction mixture allows a wide range of analyte concentrations to be handled; and (3) that the sensitivity achieved compares favourably with the best available from conventional flow-injection analysis. The limits of detection were found to be 5 ppb for NH₄ ⁺, 30 ppb for NO₃ ^-, and 4 ppb for NO₂ ^-.     

Electrochemical behavior and its electrocatalytic properties of chemically modified electrode with Keggin-type [SiNi(H2O)W11O39]

A monolayer of Keggin-type heteropolyanion [SiNi(H₂O)W₁₁O₃₉]⁶⁻ was fabricated by electrodepositing [SiNi(H₂O)W₁₁O₃₉]⁶⁻ on cysteamine modified gold electrode. The monolayer of [SiNi(H₂O)W₁₁O₃₉]⁶⁻ modified gold electrode was characterized by atomic force microscopy (AFM) and electrochemical method. AFM results showed the [SiNi(H₂O)W₁₁O₃₉]⁶⁻ uniformly deposited on the electrode surface and formed a porous monolayer. Cyclic voltammetry exhibited one oxidation peak and two reduction peaks in 1.0 M H₂SO₄ in the potential range of −0.2 to 0.7 V. The constructed electrode could exist in a large pH (0-7.6) range and showed good catalytic activity towards the reduction of bromate anion (BrO₃⁻) and nitrite (NO₂⁻), and oxidation of ascorbic acid (AA) in acidic solution. The well catalytic active of the electrode was ascribed to the porous structure of the [SiNi(H₂O)W₁₁O₃₉]6⁻ monolayer.     

Efficient Reduction of NO x by H2 Under Oxygen-Rich Conditions over Pd/TiO2 Catalysts: An in situ DRIFTS Study

The H₂/NO/O₂ reaction under lean-burn conditions has been studied by means of in situ DRIFTS, reactor measurements and temperature-programmed desorption with the aim of understanding the very different behavior of Pd/TiO₂ and Pd/Al₂O₃ catalysts. The former deliver very high NO _x conversions (70-80%) with good N₂ selectivity whereas the latter show very low activity. In addition, PdTiO₂ exhibits two distinct NO _x reduction pathways, thus greatly extending the useful temperature range. It is shown that the PdTiO₂ low-temperature channel involves adsorption and subsequent dissociation of NO on reduced (Pd⁰) metal sites. The low activity of PdAl₂O₃ is a consequence of palladium remaining in an oxidized state under reaction conditions. The high-temperature NO reduction channel found with PdTiO₂ is associated with the generation and subsequent reaction of NH _x species.     

Catalytic reduction of NH4NO3 by NO: Effects of solid acids and implications for low temperature DeNOx processes

Ammonium nitrate is thermally stable below 250 °C and could potentially deactivate low temperature NO_x reduction catalysts by blocking active sites. It is shown that NO reduces neat NH₄NO₃ above its 170 °C melting point, while acidic solids catalyze this reaction even at temperatures below 100 °C. NO₂, a product of the reduction, can dimerize and then dissociate in molten NH₄NO₃ to NO⁺ + NO₃⁻, and may be stabilized within the melt as either an adduct or as HNO₂ formed from the hydrolysis of NO⁺ or N₂O₄. The other product of reduction, NH₄NO₂, readily decomposes at ≤100 °C to N₂ and H₂O, the desired end products of DeNO_x catalysis. A mechanism for the acid catalyzed reduction of NH₄NO₃ by NO is proposed, with HNO₃ as an intermediate. These findings indicate that the use of acidic catalysts or promoters in DeNO_x systems could help mitigate catalyst deactivation at low operating temperatures (<150 °C).     

Solubilities in the ammonium thiosulfate-urea-ammonium nitrate-water system at 0°C

Solubilities in the system CO(NH₂)₂-NH₄NO₃-(NH₄)₂S₂O₃-H₂O were obtained at 0°C and pH values between 6.12 and 7.33. The new composition of matter, (NH₄)₆(S₂O₃)₂(NO₃)₂·CO(NH₂)₂, was identified and characterized chemically and microscopically. Stable high-analyses solution fertilizers can be produced at 0°C utilizing waste ammonium thiosulfate solutions with standard ammonium nitrate and urea fertilizer materials. A 31-0-0-5.6S grade (%N-%P₂O₅-%K₂O-Other) fertilizer solution can be formed at 0°C when NH₄NO₃/CO(NH₂)₂ is about one. Stable 30% total nitrogen solutions containing up to 10% sulfur can be produced at other NH₄NO₃/CO(NH₂)₂ ratios.     

Electrocatalytic reduction of nitrate on copper electrode in alkaline solution

This work is devoted to the study of the kinetics and reaction mechanism of nitrate reduction on a copper electrode in 0.1 M NaOH, which acts as the supporting electrolyte. The experimental methods include cyclic voltammetry (CV), cronoamperometry (CA), controlled-potential electrolysis (CPE), and coulometry. In CV, there are three potential regions where charge transfer reactions take place, reactions which are associated with NO₃⁻ and/or intermediates reduction. Two isopotential points observed in CV indicate the existence of some competitive adsorption processes at the electrode surface.The three charge transfer steps were also made evident in the CA, CPE and coulometry studies. The correlation of the experimental results with the literature data led to the conclusion that NO₃⁻ reduction on a copper electrode in 0.1 M NaOH has an intermediate (N₂O₂²⁻) species, which reduces to N₂ at a potential of about −1.3 V and to NH₄OH at potential values lower than −1.4 V (both values are vs. SCE).     

亚硝酸盐对聚磷菌反硝化除磷代谢及N2O产生的影响

以乙酸钠/丙酸交替为碳源的强化生物除磷(enhance biological phosphorus removal, EBPR)系统为研究对象,母反应器内种泥在厌氧/好氧的运行条件下已培养340 d,聚磷菌富集纯度达到92%±3%,考察了不同浓度亚硝酸盐氮(44.64、70.3、94.33、112.36 mg NO₂^--N·L^-1)为电子受体对聚磷菌缺氧吸磷代谢的影响。结果表明,从未经缺氧驯化的高纯度聚磷菌也可以进行反硝化除磷代谢。在缺氧反应过程中NO₂^--N还原速率、PO₄^3--P吸收速率、PHA降解速率随着亚硝酸浓度升高呈下降趋势,但是在初始亚硝酸盐氮浓度最高为112.36 mg NO₂^--N·L^-1条件下,代谢并未停止,此时亚硝酸盐还原速率与磷酸盐吸收速率仍可以分别达到2.61 mg NO₂^--N·(g MLSS)^-1·h^-1和3.0 mg PO₄^3--P·(g MLSS)^-1·h^-1。聚磷菌在以细胞内PHA作为碳源以NO₂^--N作为电子受体反硝化除磷代谢过程中,由于初始亚硝酸盐的抑制作用使NO₂^--N还原速率大于N₂O还原速率,从而产生大量的N₂O积累。初始投加NO₂^--N浓度为44.64、70.3、94.33、112.36 mg NO₂^--N·L^-1时,产生的N₂O占TN的比例分别为63.5%、49.0%、30.2%、24.0%。在底物充足的条件下,代谢中积累的N₂O可以通过延长缺氧搅拌时间,使其转化为N₂。     

Effects of specific adsorption of copper (II) ion on charge transfer reaction at the thin film LiMn2O4 electrode/aqueous electrolyte interface

This study investigated the effect of a specific adsorption ion, copper (II) ion, on the kinetics of the charge transfer reaction at a LiMn₂O₄ thin film electrode/aqueous solution (1 mol dm⁻³ LiNO₃) interface. The zeta potential of LiMn₂O₄ particles showed a negative value in 1 × 10⁻² mol dm⁻³ LiNO₃ aqueous solution, while it was measured as positive in the presence of 1 × 10⁻² mol dm⁻³ Cu(NO₃)₂ in the solution. The presence of copper (II) ions in the solution increased the charge transfer resistance, and CV measurement revealed that the lithium insertion/extraction reaction was retarded by the presence of small amount of copper (II) ions. The activation energy for the charge transfer reaction in the solution with Cu(NO₃)₂ was estimated to be 35 kJ mol⁻¹, which was ca. 10 kJ mol⁻¹ larger than that observed in the solution without Cu(NO₃)₂. These results suggest that the interaction between the lithium ion and electrode surface is a factor in the kinetics of charge transfer reaction.     

Effect of hydroxyl and nitrate ions on the sorption of ammonium ions by sulphonic cation exchangers

The sorption of ammonium ions and ammonia by the H+ form of sulphonic acid cation exchangers Amberlite 252, Lewatit 2629 and Relite C 360 from a solution containing NH₄NO₃ in the range of 0 to 0.214 equ/L and NH₃ in the range of 0.353 to 0 equ/L was investigated to establish the possibility of their application for the recovery of ammonium from caustic condensate generated in nitrogen fertilizer production. Breakthrough and elution curves were obtained, determining the concentration of ammonium with Nessler's reagent. The sorption of ammonium and ammonia depends on the concentration ratio of ammonia to ammonium nitrate [NH₃]/[NH₄NO₃]. On decreasing [NH₃]/[NH₄NO₃], the concentration ratio of hydroxyl to nitrate ions [OH⁻]/[NO⁻₃] and the effluent pH prior to NH⁺₄ breakthrough also decrease. This results in a decrease in the NH⁺₄ sorption because of a deficiency in the neutralization of hydrogen ions released (ordinary cation-exchange process). Thus, adverse circumstances create an unfavorable medium for NH⁺₄ removal from the caustic condensate. Maximum sorption of NH⁺₄ is attained at [NH₃]/[NH₄NO₃] ∼1.2. A further decrease in [NH₃]/[NH₄NO₃] is followed by a significant decrease in the effluent pH, which leads to an increase in the concentration of protonated sulphonic acid groups (-SO₃H), resulting in a decrease in the ion-exchange ability of the cation exchangers under investigation with respect to NH⁺₄ removal. The concentration (g/L) of NH₄NO₃ in the eluate from the cation-exchanger regeneration, carried out using 0.7 bed volumes (BV) of 20% HNO₃, amounts to 136.7 for Relite C 360, 119.5 for Lewatit K 2629 and 96.7 for Amberlite 252. The content of undamaged beads after 100 cycles (each cycle comprises saturation with caustic condensate, containing ammonia and ammonium, successive regeneration with 20% nitric acid and washing) is from 97 to 99.8%. Resistance to boiling in 20% HNO₃ solution is from 97 to 99.8%. These are applicable for the recovery of NH₄NO₃ from the caustic condensate in the nitrogen fertilizers production, preventing economic damage and environmental contamination from nitrogen compounds.     

Thermal Analysis of Ammonium Dinitramide Decomposition

The new energetic material ammonium dinitramide (ADN), NH₄N(NO₂)₂, has been investigated with regard to its thermal properties and decomposition behavior. Thermal decomposition of ADN is observed after complete melting at 91.5 °C. The main decomposition pathway is based on the formation of NH₄NO₃ and N₂O followed by the thermal decomposition of NH₄NO₃ to N₂O and H₂O at higher temperatures. Side reactions forming NO₂, NO, NH₃, N₂ and O₂ are described and a mechanism for the acid-catalized decomposition of hydrogen dinitramide, dissociation product of ADN, is proposed.