Inorganic Ammonium Salts Research Articles

Inorganic ammonium salt doping in nickel oxide for highly efficient planar perovskite solar cells

Inorganic ammonium salt doping in nickel oxide for highly efficient planar perovskite solar cells

Study on the effect of conditioner on NOx precursor control behavior from sewage sludge pyrolysis: Focusing on conditioner assessments and in-situ fixation mechanism

The nitrogen transformation during sludge pyrolysis is affected by the dewater conditioner. However, the comparative analysis of the conditioner under identical pyrolysis conditions has been previously absent. In this study, Ca-, Fe- and Al-based conditioners were selected as the representatives. A comprehensive evaluation considering the cost of the conditioners and the product characteristics was conducted. Additionally, the in-situ fixation mechanism of the conditioner on nitrogen-containing gas was concurrently revealed. Among the six conditioners, CaO and AlCl3 were identified as the top performers, ranking first and second, respectively. Furthermore, Fe/Ca-based conditioners reduced NH3 and HCN release by 1.5 ∼ 5.53 % and 0 ∼ 1.55 %, respectively, by facilitating the conversion of amine-N to a more stable form in condensable fraction. Fe promoted volatile amine-N cyclization, while Ca encouraged its dehydrogenation. Both Fe/Ca-based conditioners increased 7.5 ∼ 14.8 % nitrogen retention in char, by inhibiting the decomposition of protein-N. Al-based conditioners had little effect on NH3 and HCN, but contributed to 2.3 ∼ 2.8 % production of stabilized nitrogen in char. The introduction of Cl in Fe/Ca/Al chloride conditioners would promote the decomposition of inorganic ammonium salts to produce NH3 at 30 ∼ 185 °C. And Cl also reacted with volatiles through electrophilic substitution reaction, leading to the formation of halogenated hydrocarbons in condensable fraction and the release of more NH3, HCN, and HNCO at 30 ∼ 465 °C. The findings of this study provide a detailed comparative analysis of various conditioners under uniform conditions and reveal the in-situ fixation mechanism of nitrogen-containing gas. This will provide guidance for the sludge conditioning-dewatering-drying integrated treatment and disposal.

Enhancing characterization of organic nitrogen components in aerosols and droplets using high-resolution aerosol mass spectrometry

Abstract. This study aims to enhance the understanding and application of the Aerodyne high-resolution aerosol mass spectrometer (HR-AMS) for the comprehensive characterization of organic nitrogen (ON) compounds in aerosol particles and atmospheric droplets. To achieve this goal, we analyzed 75 N-containing organic compounds, representing a diverse range of ambient non-organonitrate ON (NOON) types, including amines, amides, amino acids, N heterocycles, protein, and humic acids. Our results show that NOON compounds can produce significant levels of NHx+ and NOx+ ion fragments, which are typically recognized as ions representative of inorganic nitrogen species. We also identified the presence of CH2N+ at m/z = 28.0187, an ion fragment rarely quantified in ambient datasets due to substantial interference from N2+. As a result, the utilization of an updated calibration factor of 0.79 is necessary for accurate NOON quantification via the HR-AMS. We also assessed the relative ionization efficiencies (RIEs) for various NOON species and found that the average RIE for NOON compounds (1.52 ± 0.58) aligns with the commonly used default value of 1.40 for organic aerosol. Moreover, through a careful examination of the HR-AMS mass spectral features of various NOON types, we propose fingerprint ion series that can aid the NOON speciation analysis. For instance, the presence of CnH2n+2N+ ions is closely linked with amines, with CH4N+ indicating primary amines, C2H6N+ suggesting secondary amines, and C3H8N+ representing tertiary amines. CnH2nNO+ ions (especially for n values of 1–4) are very likely derived from amides. The co-existence of three ions, C2H4NO2+, C2H3NO+, and CH4NO+, serves as an indicator for the presence of amino acids. Additionally, the presence of CxHyN2+ ions indicates the occurrence of 2N-heterocyclic compounds. Notably, an elevated abundance of NH4+ is a distinct signature for amines and amino acids, as inorganic ammonium salts produce only negligible amounts of NH4+ in the HR-AMS. Finally, we quantified the NOON contents in submicron particles (PM1) and fog water in Fresno, California, and PM1 in New York City (NYC). Our results revealed the substantial presence of amino compounds in both Fresno and NYC aerosols, whereas concurrently collected fog water in Fresno contained a broader range of NOON species, including N-containing aromatic heterocycle (e.g., imidazoles) and amides. These findings highlight the significant potential of employing the widespread HR-AMS measurements of ambient aerosols and droplets to enhance our understanding of the sources, transformation processes, and environmental impacts associated with NOON compounds in the atmosphere.

Organophotocatalysed synthesis of 2-piperidinones in one step via [1 + 2 + 3] strategy

Six-membered N-containing heterocycles, such as 2-piperidinone derivatives, with diverse substitution patterns are widespread in natural products, drug molecules and serve as key precursors for piperidines. Thus, the development of stereoselective synthesis of multi-substituted 2-piperidinones are attractive. However, existing methods heavily rely on modification of pre-synthesized backbones which require tedious multi-step procedure and suffer from limited substitution patterns. Herein, an organophotocatalysed [1 + 2 + 3] strategy was developed to enable the one-step access to diverse substituted 2-piperidinones from easily available inorganic ammonium salts, alkenes, and unsaturated carbonyl compounds. This mild protocol exhibits exclusive chemoselectivity over two alkenes, tolerating both terminal and internal alkenes with a wide range of functional groups.

Liquid–Liquid Demixing Behavior of Aqueous 1-Butanol Solutions in the Presence of Various Organic and Inorganic Ammonium Salts: Effect of Temperature, Cation Alkyl Chain Length, and Anion Type of Salts on Salting Coefficients and Thermodynamic Functions

Liquid–Liquid Demixing Behavior of Aqueous 1-Butanol Solutions in the Presence of Various Organic and Inorganic Ammonium Salts: Effect of Temperature, Cation Alkyl Chain Length, and Anion Type of Salts on Salting Coefficients and Thermodynamic Functions

Catalytic cracking of supercritical n-dodecane over macro-meso-HZSM-5 coatings by vertical secondary growth

Hierarchical HZSM-5 zeolite coatings are extensively investigated for catalytic cracking of supercritical fuels to benefit the thermal management of hypersonic aircraft. However, there is still a challenge for preparing zeolite coatings combining the high diffusion property, strong mechanical strength and a large amount of Brønsted acid sites. Herein, the macro-meso-HZSM-5 coatings with meso-HZSM-5 grains vertically welding on the compact and randomly oriented zeolite basal layer were fabricated on the inner wall of the stainless-steel tubes by ammonia-assisted vertical secondary growth, using amphiphilic organosilane as a meso-porogen. The structure benefited the breaking of the trade-off between diffusion and acidity of the coating. And by adjusting the dosage of inorganic ammonium salt and the crystallization time, the synthesis mechanism of the coatings was speculated. Inorganic ammonium salt facilitated the formation of macropores and the vertical growth of crystals with (00 h)&(10 h) orientation (pseudo-c-orientation). The chemical composition of the seed layer was adjusted using Si-MFI, Al-MFI or Ga-MFI as seeds, and the mechanical strength was enhanced by the intergrowth of zeolite phase in the seed layer. The macro-meso-HZSM-5 coating synthesized with Al-MFI as the seed (MZC-Al-2N), exhibited an excellent catalytic conversion and stability for cracking of supercritical n-dodecane (550 °C and 4 MPa), with the initial reaction rate and the deactivation rate being three times and 52 % of the conventional HZSM-5 coating, respectively, due to the combination of the improved diffusion property as well as the suitable acidity. The coating synthesized using Ga-MFI seed showed a lower activity, but a higher heat sink compared with MZC-Al-2N, probably due to the dehydrogenation of light alkanes over the synergistic effect between the Brønsted acid sites and the extra-framework Ga species.

Three-component selective synthesis of phenothiazines and bis-phenothiazines under metal-free conditions.

An iodine-containing reagent promoted three-component method for the selective synthesis of phenothiazines and bis-phenothiazines has been developed. The present protocol starts from simple and easily available cyclohexanones, elemental sulfur, and inorganic ammonium salts, selectively producing phenothiazines and bis-phenothiazines in satisfactory yields under aerobic conditions. This method has the advantages of simple and readily available starting materials and metal-free conditions, affording a facile and practical approach for the preparation of phenothiazines and bis-phenothiazines.

Optimizing NH4+ Storage Capability of Nickel Ferrocyanide by Regulating Coordination Anion in Aqueous Electrolytes

AbstractWill anions in electrolytes affect the electrochemical properties of Prussian blue analogues for aqueous ammonium ion batteries? In this study, the electrochemical reaction between nickel ferrocyanide and ammonium ions is investigated in three common inorganic ammonium salt solutions [NH4NO3, NH4Cl, and (NH4)2SO4]. The results suggest that at the same NH4+ concentration, nickel ferrocyanide exhibits different electrochemical performances. The as‐prepared nickel ferrocyanide contains two phases, which are rhombohedral phase and cubic phase. Rhombohedral phase of nickel ferrocyanide has a high reactivity in 0.5 M (NH4)2SO4 solution during cycling while cubic phase shows good performance in 1 M NH4NO3 and 1 M NH4Cl electrolyte. It should be noted that the performance of cubic phase is superior to rhombohedral phase in kinetic consideration. Additionally, due to the strong coordination ability of chloride, nickel ferrocyanide exhibits an excellent electrochemical performance in 1 M NH4NO3 solution, rather than 1 M NH4Cl electrolyte.

Sulfur-promoted, one-pot, and metal-free conversion of aromatic aldehydes to nitriles using an inorganic ammonium salt as the nitrogen source

A simple protocol for the sulfur-promoted conversion of aromatic aldehydes to aromatic nitriles has been developed. This strategy enables the one-pot conversion of inexpensive and readily available aromatic aldehydes into highly valuable aromatic nitriles using a cheap inorganic ammonium salt as the nitrogen source in the absence of metals. Significantly, a broad scope of substrates was explored using this strategy, and various groups, including alkyl, alkoxyl, alkylthiol, hydroxyl, amino, aryl, alkenyl, cyano, carboxyl, and borate ester groups were tolerated, and good to excellent yields were achieved in most cases. Additionally, polycyclic aromatic aldehydes and heteroaromatic aldehydes also could be converted to the corre-sponding nitriles with satisfactory yields. This method can be utilized as a powerful tool for the cyanation of complex molecules.

Ionic Liquids Induced Aqueous Biphasic Systems of Ppg 725 + Inorganic Ammonium Salts: Partitioning Capacity for Dyes

Ionic Liquids Induced Aqueous Biphasic Systems of Ppg 725 + Inorganic Ammonium Salts: Partitioning Capacity for Dyes

Laboratory studies of the oil-displacing capacity of multifunctional chemical composition based on surfactants

The development of deposits of hard-to-recover reserves, including heavy and high-viscosity oil, dictates the need to search for new and improve existing enhanced oil recovery methods. One of the well-known methods of increasing oil recovery is the use of reservoir treatments with chemical compositions containing surfactants. A new multifunctional chemical oil-displacing composition (MFC) capable of operating in a wide temperature range has been created at the Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences. The oil-displacing composition of MFC based on a surfactant, an adduct of inorganic acid, polyol, ammonium and aluminum salts, and urea is designed to increase the oil recovery of fields at both early and late stages of development.The article presents the results of laboratory tests of the developed MFC for enhanced oil recovery. Experiments were carried out on the setup to study the filtration characteristics of models of heterogeneous formation.As a result of experiments, it was found that the use of the MFC composition leads to a significant increase in the oil displacement coefficient at both low and high temperatures. The high oil-displacing capacity of MFC at low temperature is caused by the interaction of inorganic acid and polyol, which are part of the composition, with the formation of a strong acid that reacts with the carbonate rock of the reservoir. At high temperature, due to the processes of hydrolysis of urea and aluminum salt, MFC evolves into an alkaline composition with the formation of an alkaline buffer system (pH = 9), which is optimal for oil displacement purposes.

Design of an intercalated Nano-MoS2 hydrophobic catalyst with high rim sites to improve the hydrogenation selectivity in hydrodesulfurization reaction

The preparation of the intercalated lamellar hydrophobic nano-MoS2 (size: 60−100 nm, interlayer spacing: 0.7–1.2 nm) through the substitution of organic amine for inorganic ammonium salt and the subsequent catalytic reaction as a hydrodesulfurization catalyst is presented. The intercalated amine groups broadened the interspacing of the lamellar nano-MoS2 and promoted the formation of hydrophobic stacking structure consisting of stable monolayers. The high hydrophobicity of the nano-MoS2 monolayer catalyst was confirmed. The as-synthesized intercalated hydrophobic nano-MoS2 catalyst with lower steric hindrance and higher number of rim sites showed better hydrodesulfurization performance and higher hydrogenation route selectivity than the traditional MoS2 catalyst. The conversion of dibenzothiophene using the intercalated hydrophobic nano-MoS2 catalyst was 86 % in comparison to 23 % for the traditional MoS2 catalyst. The intercalated hydrophobic nano-MoS2 catalyst was stable in five subsequent catalytic cycles.

Leaching Process of Weathered Crust Elution-Deposited Rare Earth Ore With Formate Salts.

To strengthen the rare earth leaching process and weaken the hydration of clay minerals for preventing landslides, it is of great importance to adopt a green and sustainable leaching agent in the industry. In this work, the leaching process of weathered crust elution-deposited rare earth ores with formate salts (ammonium formate, potassium formate, and sodium formate) was investigated. The effects of formate salts on the linear swelling ratio and zeta potential of the clay minerals were studied. The experimental results showed that ammonium formate could effectively recover the rare earth elements from weathered crust elution-deposited rare earth as well as inhibit the leaching of impurity aluminum. At room temperature, when the ammonium formate concentration was 1% wt, the leaching efficiencies of rare earth and aluminum were 87 and 37%, respectively. Compared with traditional inorganic ammonium salts, the inhibition effect of impurity aluminum was obvious. In addition, the results of the linear swelling ratio in the clay minerals showed that the inhibit ability of formate salts on the hydration of clay minerals enhanced with the increase of the formate concentration, and the order of the inhabitation on the clay minerals followed: 1% ammonium formate > 1.5% potassium formate > 2.5% sodium formate > distilled water. Based on the double layer theory, ammonium formate and potassium formate could effectively compress clay mineral particles to avoid water intake, which could increase the interaction between clay mineral particles and greatly reduce the electronegative property of the clay minerals, so as to effectively reduce the surface hydration of clay minerals to decrease the swelling of rare earth ore. The results of this experiment have important and practical significance in guiding the prevention of landslides, promoting the in-situ leaching technology, and effectively protecting the ecological environment in mining areas.

ВЫДЕЛЕНИЕ ЭМУЛЬСИОННОГО КАУЧУКА ИЗ ЛАТЕКСА С ПРИМЕНЕНИЕМ СОЛЕЙ ГИДРОКСИЛАМИНОВ

Currently, there is a growth of industry in various sectors, including chemical and petrochemical in Russia and abroad. However, this rise in industry is inextricably linked to the emergence of environmental problems. Therefore, when developing new technologies, production facilities and improving existing ones, special attention is paid to their environmental aspect. These industries include the production of synthetic rubbers. The production of synthetic rubber is a multi-stage technology; at some stages certain problems are observed. For example, the coagulation stage is characterized by increased contamination of wastewater with residues of coagulating, acidifying agents and components of the emulsion system. Therefore, research in the direction of improving the environmental friendliness of this stage is important and relevant. Research on the search for new promising coagulants has been carried out. A comparative assessment of the coagulating ability of ammonium salts based on hydroxylamine hydrochloric acid and sulfuric acid in comparison with ammonium chloride and sulfate and sodium chloride is carried out. The effectiveness of the coagulating action of these inorganic ammonium salts is studied on industrial rubber latex SKS-30 ark. It is found that the yield of rubber crumbs naturally increased with a growth in the consumption of the coagulating agent and a decrease in the temperature regime of the process. Positive results are achieved when nitrogen-containing salts are used to reduce the aggregative stability of disperse systems. Сaoutchouc and rubbers in their basic indicators meet the requirements.

FEATURES OF BEHAVIOR OF ORGANIC AMMONIUM SALTS WHEN ISOLATING RUBBER FROM LATEX

The influence of low-and high-molecular substances on the stability of various lyophobic colloidal systems is among the earliest empirical and intuitively used phenomena. The water-soluble organic salts are applied in different industries including latex technology. This is related to a complex of various colloid-chemical phenomena and their interaction with latex dispersed phase and its components. Nowadays some high-molecular and low-molecular organic reagents are used to reduce the aggregate stability of latex system on an industrial scale. In the article, the coagulating ability of ammonium acetate, ammonium oxalate and ammonium citrate were estimated for the latex coagulation in the comparison with an inorganic ammonium salt and sodium chloride. The influence of the nature of salt component, as well as its consumption, on the technological features of the coagulation process in the emulsion latex was established. The relationship between the consumption of organic ammonium salt and acidifying component on the complete coagulation was shown. It’s worth noting that the strength of the acid, which forms the ammonium salt, has an effect on the technological extraction process of rubber from latex. The stronger the organic acid, the lower the consumption of the acidifying agent, and complete coagulation is achieved at lower consumption of coagulants. Peculiar behavior of ammonium citrate has been noted: complete coagulation wasn’t achieved with the consumption of this salt over 200 kg/t of rubber and increased consumption of the acidifying agent. It can be due to the fact that citric acid is an oxyacid and shows properties characteristic for surfactants and increases the aggregate stability of the system. These rubbers, rubber compounds and vulcanizates obtained correspond to standard parameters.

Investigation of pathways for transformation of N‑heterocycle compounds during sewage sludge pyrolysis process

This study investigated the transformation of N‑heterocycle compounds during sewage sludge pyrolysis process. The reaction pathways for evolution of the products especially the N-containing organics such as amino acids‑N were analyzed in detail. NH3 is the main N-containing gaseous product during the pyrolysis and its concentration was increased with the increasing temperature. Phenolic compounds, hydrocarbons and heterocyclic compounds were the main component in liquid products. The in situ FT-IR study showed that the labile inorganic ammonium salt decomposition proceeded to completion below 500 °C. Above 500 °C N‑heterocycle compound was formed and then it was decomposed, while above 600 °C nitrile started to decompose. NH3 formation main originates from the decomposition of N‑heterocyclic compounds and nitrile. Proteins during the pyrolysis, as verified by XPS, were mainly converted into inorganic nitrogen. In addition, the Py-GC–MS results showed that large amount of N‑heterocyclic compounds were found in amino acid‑N pyrolysis products. The transformation paths for the amino acids with different chemical structures were distinct. Except N‑heterocyclic amino acids, long chain aliphatic amino acid also can form N‑heterocyclic compounds through cyclization. In addition, the decomposition of the intermediates of N‑heterocyclic compounds form small molecular compounds or while the polymerization of the intermediates forms macromolecule compounds. The amino acids with heterocycle structure were disrupted to form heterocycle and aliphatic intermediate. The plausible mechanism of sewage sludge pyrolysis was proposed.

Salting-in and salting-out effects of organic and inorganic ammonium salts on the aqueous polymer solutions

This paper accomplishes a broad survey of the salting effects of different ammonium salts on the aqueous polymer solutions. In order to cover a wide range of hydrophilic and hydrophobic nature of solutes, salts including ammonium chloride (NH4Cl), ammonium bromide (NH4Br), tetraethyl ammonium bromide (TEAB), tetrapropyl ammonium bromide (TPAB), tetrabutyl ammonium bromide (TBAB), tetrabutyl ammonium chloride (TBAC), and dodecyl trimethyl ammonium bromide (DTAB), and polymers polyethylene glycol (PEG400 and PEG10000) and polypropylene glycol (PPG400 and PPG1000) have been used. In the first part of this work, cloud point temperatures (TC) for binary system of PPG1000 in pure water and for ternary systems of PPG1000 in aqueous solutions of ammonium salts have been determined by visual observation. It is shown that while the inorganic ammonium salts (NH4Cl and NH4Br) reduce the TC values of PPG1000 aqueous solutions (salting-out effect), the organic ammonium salts (TEAB, TPAB, TBAB, TBAC, DTAB) because of hydrocarbon portions in their structure favourably interact with PPG1000 and elevate the TC values (salting-in effect). The values of salting coefficient and energetic parameters of clouding process have been calculated. In the second part of this work, the isopiestic equilibrium has been investigated for several ternary {polymer + ammonium salt + water} systems at 298.2 K. Three different types of constant water activity curves deviation from the linear isopiestic relation (LIR) were observed: negative deviations for systems which undergo salting-out phenomenon and phase separation, positive deviations for systems which undergo salting-in effect, and non-deviation for semi-ideal solutions. The effects of type and molar mass of polymers, and type of cation and anion of ammonium salts on the magnitude and type of salting effects have been scrutinized.

The hydrolysis of epoxides catalyzed by inorganic ammonium salts in water: kinetic evidence for hydrogen bond catalysis.

Naturally-occurring inorganic ammonium ions have been recently reported as efficient catalysts for some organic reactions in water, which contributes to the understanding of the chemistry in some natural environments (soils, seawater, atmospheric aerosols, …) and biological systems, and is also potentially interesting for green chemistry as many of their salts are cheap and non-toxic. In this work, the effect of NH4+ ions on the hydrolysis of small epoxides in water was studied kinetically. The presence of NH4+ increased the hydrolysis rate by a factor of 6 to 25 compared to pure water and these catalytic effects were shown not to result from other ions, counter-ions or from acid or base catalysis, general or specific. The small amounts of amino alcohols produced in the reactions were identified as the actual catalysts by obtaining a strong acceleration of the reactions when adding these compounds directly to the epoxides in water. Replacing the amino alcohols by other strong hydrogen-bond donors, such as trifluoroethanol (TFE) or hexafluoroisopropanol (HFIP) gave the same results, demonstrating that the kinetics of these reactions was driven by hydrogen-bond catalysis. Because of the presence of many hydrogen-bond donors in natural environments (for instance amines and hydroxy-containing compounds), hydrogen-bond catalysis is likely to contribute to many reaction rates in these environments.

Study on the nitrogen transformation during the primary pyrolysis of sewage sludge by Py-GC/MS and Py-FTIR

The nitrogen transformation with attention to the intermediates and NOx precursors has been investigated during the primary pyrolysis of sewage sludge by using Pyrolyzer-gas chromatography/mass spectrometry (Py-GC/MS) and Pyrolyzer-Fourier transform infrared spectrometry (Py-FTIR). A three-stage process of nitrogen transformation during the sewage sludge pyrolysis was suggested. The decomposition of labile protein and inorganic ammonium salt mainly occurred in the first stage (<300 °C), giving rise to a small amount of NH3. In the second stage (300–600 °C), the macromolecular protein firstly cracked into small molecular amine compounds, and then went through deamination process, contributed to a large release of NH3. In the third stage (600–900 °C), the amine compounds converted into nitriles, and generated a large amount of HCN, while the formation of NH3 slowed down accordingly.

Ambient and laboratory observations of organic ammonium salts in PM1.

Ambient measurements of PM1 aerosol chemical composition at Cabauw, the Netherlands, implicate higher ammonium concentrations than explained by the formation of inorganic ammonium salts. This additional particulate ammonium is called excess ammonium (eNH4). Height profiles over the Cabauw Experimental Site for Atmospheric Research (CESAR) tower, of combined ground based and airborne aerosol mass spectrometric (AMS) measurements on a Zeppelin airship show higher concentrations of eNH4 at higher altitudes compared to the ground. Through flights across the Netherlands, the Zeppelin based measurements furthermore substantiate eNH4 as a regional phenomenon in the planetary boundary layer. The excess ammonium correlates with mass spectral signatures of (di-)carboxylic acids, making a heterogeneous acid-base reaction the likely process of NH3 uptake. We show that this excess ammonium was neutralized by the organic fraction forming particulate organic ammonium salts. We discuss the significance of such organic ammonium salts for atmospheric aerosols and suggest that NH3 emission control will have benefits for particulate matter control beyond the reduction of inorganic ammonium salts.