Alkylammonium Chlorides Research Articles

Highly Efficient Pure‐Red Quasi‐2D Perovskite Light‐Emitting Diodes Enabled by Propylammonium Chloride Passivator

AbstractPerovskite light‐emitting diodes (PeLEDs) based on quasi‐2D perovskites have attracted great attention in the past few years. Although significant achievements are made in device performance, fabrication of high‐efficiency PeLEDs with pure‐red (620–635 nm) light emission remains a significant challenge, which inhibits their practical application for full‐color displays. Herein, a series of efficient red PeLEDs at 625 nm are realized by employing volatile alkylammonium chlorides (propylammonium chloride) passivators. The interaction of PbI2 with propylamine (PA)…H+Cl− in the precursor solution effectively passivates the defects, leading to reduced non‐radiative recombination and enhanced device performance. By optimizing the amount of PACl, an external quantum efficiency (EQE) of 16.1% and a maximum brightness of 1701 cd m−2 are achieved, among the best‐performing quasi‐2D I‐based PeLEDs with emissions ranging from 620 to 635 nm. This work provides a new route to improve the stability and efficiency of pure‐red PeLEDs.

Gel‐Derived Amorphous Precursor Enables Homogeneous Pure‐Phase α‐FAPbI3 Films for Efficient and Stable Perovskite Solar Cells

AbstractPure‐phase α‐formamidinium lead iodide (α‐FAPbI3) perovskite solar cells (PSCs) possess potential high efficiency because of suitable bandgap. However, achieving high‐quality α‐FAPbI3 films during the spin‐coating process is challenging without anti‐solvent extraction, due to the spontaneous formation of the more stable δ‐FAPbI3 phase and the complexity of multi‐component perovskite precursor solutions. Here a gel precursor with an amorphous structure to eliminate the need for anti‐solvent extraction in achieving the homogeneous and highly oriented pure‐phase α‐FAPbI3 is devised films. The incorporation of N,N′‐dimethylpropyleneurea, and alkylammonium chloride results in extended iodoplumbate clusters in the perovskite precursor solution. In situ, spectroscopic analysis reveals that the emergence of the stable amorphous gel precursor during the initial solidification stage ensures a uniform solute distribution. This effectively prevents preferentially oriented growth in the crystal phase precursor, leading to a significant enhancement in film homogeneity. As a result, power conversion efficiencies of 24.17% for the PSC, and 19.3% for the module are achieved, along with superior operational stability, retaining 96.1% of their initial efficiency after 850 h at the maximum power point tracking. These demonstrate the best performance for the reported pure‐phase α‐FAPbI3 PSCs without anti‐solvent extraction, showing great promise for scalable manufacture.

Synergistic Effect of Alkylammonium Chlorides to Trigger an Ultrafast Nucleation for Antisolvent‐Free Perovskite Solar Cells Processed from 2‐Methoxyethanol

Abstract2‐Methoxyethanol (2ME), as a more environmentally friendly solvent with a lower boiling point compared to dimethylformamide, is ideal for the fabrication of perovskite solar cells (PSCs). However, when 2ME is used for antisolvent‐free deposition of perovskite films, an uncontrolled nucleation process and an easy phase transition to the δ‐phase often occur. Herein, an ultrafast nucleation process is developed using methylamine chloride (MACl) and n‐butylammonium chloride (BACl) as dual additives in 2ME without further solvent addition. While MACl can rapidly induce MACl‐based nuclei to initiate the nucleation process for formamidinium lead iodide (FAPbI3), the addition of BACl to the precursor with MACl can further increase the nucleation rate and density of nuclei, and bypass the transition from δ‐ to α‐phase during crystal growth to obtain a highly crystalline and pinhole‐free perovskite film. As a result, the FAPbI3 PSCs achieve a power conversion efficiency (PCE) of 23.6%. This work provides a new inspiration for controlling the crystal quality of perovskite thin films via nucleation rate suitable for upscaling.

Efficient Carbon‐Based Perovskite Solar Cells Passivated by Alkylammonium Chloride

Hole‐transport layer (HTL)‐free carbon‐based perovskite solar cells (C‐PSCs) have garnered significant attention in the research community due to their cost‐effectiveness and high stability. However, the absence of a traditional HTL can lead to substantial nonradiative recombination of charge carriers between the perovskite layer and the carbon electrode, significantly impacting efficiency. Herein, the performance effects of different alkylammonium chlorides, including butylammonium chloride, octylammonium chloride, and dodecylammonium chloride (DACl), on perovskite (FA0.1MA0.9PbI3) are investigated to produce high‐performance HTL‐free C‐PSCs. Following passivation, the film exhibits a more uniform grain size distribution and fewer grain boundary defects. Furthermore, with an increase in the alkyl chain length, enhanced interactions with the perovskite film result in reduced trap state density and increased carrier lifetime. After DACl passivation, the C‐PSC achieves a remarkable power conversion efficiency of 16.56% and a high open‐circuit voltage (Voc) of 1.074 V. The Voc enhancement is primarily attributed to the better energy‐level alignment, effectively improving hole transport and electron‐blocking capabilities while suppressing nonradiative recombination. Additionally, they demonstrate exceptional hydrophobic characteristics and robust stability in the presence of humidity, making them particularly promising for future practical applications in the field of photovoltaics.

Liquid–liquid phase separation in binary mixtures of quaternary alkylammonium chlorides with carboxylic acids

We reported the phase separation measurements of mixtures obtained from choline, tetramethylammonium and tetraethylammonium chlorides with methacrylic (MAA), butyric (BA) and isobutyric (IBA) acids as solvents. Liquid-liquid equilibrium (LLE) experiments were performed under atmospheric pressure in a temperature range of 287–403 K using cloud-point method and the data were correlated with the Non-Random Two Liquid (NRTL) solution model. The density, the viscosity, the Kamlet-Taft and the solvent polarity (ET(30)) parameters were measured for coexisting liquid phases. The applicability of the obtained binary biphasic system in extraction process, particularly purification of MAA from a phenolic inhibitor, was demonstrated.

Alkylammonium chloride promotes the record efficiency of perovskite solar cells

Alkylammonium chloride promotes the record efficiency of perovskite solar cells

Controlled growth of perovskite layers with volatile alkylammonium chlorides.

Controlling the crystallinity and surface morphology of perovskite layers by methods such as solvent engineering1,2 and methylammonium chloride addition3-7 is an effective strategy for achieving high-efficiency perovskite solar cells. In particular, it is essential to deposit α-formamidinium lead iodide (FAPbI3) perovskite thin films with few defects due to their excellent crystallinity and large grain size. Here we report the controlled crystallization of perovskite thin films with the combination of alkylammonium chlorides (RACl) added to FAPbI3. The δ-phase to α-phase transition of FAPbI3 and the crystallization process and surface morphology of the perovskite thin films coated with RACl under various conditions were investigated through in situ grazing-incidence wide-angle X-ray diffraction and scanning electron microscopy. RACl added to the precursor solution was believed to be easily volatilized during coating and annealing owing to dissociation into RA0 and HCl with deprotonation of RA+ induced by RA⋯H+-Cl- binding to PbI2 in FAPbI3. Thus, the type and amount of RACl determined the δ-phase to α-phase transition rate, crystallinity, preferred orientation and surface morphology of the final α-FAPbI3. The resulting perovskite thin layers facilitated the fabrication of perovskite solar cells with a power-conversion efficiency of 26.08% (certified 25.73%) under standard illumination.

Alkyl Ammonium Chloride Salts for Efficient Chlorine Storage at Ambient Conditions

Alkyl Ammonium Chloride Salts for Efficient Chlorine Storage at Ambient Conditions

From Academia to the Market - Air-stable Ni(ii)/Josiphos Catalysts.

The design, synthesis, commercialization and application of air-stable Ni(II)/Josiphos complexes has been realized in a collaboration between Solvias and ICBMS (University Lyon 1). The Ni-complexes are utilized as versatile precatalysts for diverse cross-coupling reactions. Apart from being active in established C-C and C-N couplings at low catalyst loadings, the novel Ni-precatalysts enabled the development of the challenging monoarylation of ammonia, ammonia surrogates and even alkylammonium chlorides with aryl carbamates. Finally, the α-arylation of acetone with aryl chlorides, carbamates and pivalates was demonstrated using the Ni(II)/Josiphos precatalysts.

Comparison of durability of treated wood using stake tests and survival analysis

The stake test is widely used to evaluate the efficacy of wood preservatives. This test monitors the deterioration level observed in treated stakes partially inserted into the ground. The results are conventionally expressed as the relationship between deterioration levels and exposure periods. The preservative efficacy is compared among the stake groups treated with different retention levels based on the test results; however, there is no scientific basis for the comparison. We applied survival analysis to the conventional stake test to include a scientific basis to the test. Stakes impregnated with different types and retention levels of preservatives were subjected to deterioration at two test sites for approximately 30 years. The deterioration levels were monitored according to the conventional procedure and survival analysis was applied to the monitored data. Kaplan–Meier plots of the survival probabilities against the exposure periods indicated that there is a significant difference between the durability of the stakes treated with alkylammonium chloride (AAC-1) at K2 and K3 retention levels, whereas no significant difference was observed between those at K3 and K4 retention levels. Contrastingly, emulsified copper naphthenate (NCU-E) was found to be a reliable preservative, and the stakes impregnated with NCU-E showed a significant increase in durability in accordance with preservative retention. Alkaline copper quaternary (ACQ-1) also appeared to be a reliable preservative; however, the increase in stake durability after ACQ-1 treatment differed between the test sites. These results were verified using the modified Gehan–Breslow–Wilcoxon test with Holm’s p adjusting method.

Selective Chloride-Mediated Neat Ethanol Oxidation to 1,1-Diethoxyethane via an Electrochemically Generated Ethyl Hypochlorite Intermediate

Selective primary alcohol oxidation to form aldehydes products without overoxidation to carboxylic acids remains a key chemistry challenge. Using simple alkylammonium chloride as the electrolyte with a glassy carbon working electrode in neat ethanol solvent, 1,1-diethoxyethane (DEE) was prepared with >95% faradaic efficiency (FE). DEE serves as a storage platform protecting acetaldehyde from overoxidation and volatilization. UV-vis spectroscopy shows that the reaction proceeds through an ethyl hypochlorite intermediate as the sole chloride oxidation product, and that this intermediate decomposes unimolecularly (rate constant k = (6.896 ± 0.516) × 10-4 s-1) to form HCl catalyst and acetaldehyde, which undergoes rapid nucleophilic attack by ethanol solvent to form the DEE product. This indirect oxidation mechanism enables ethanol oxidation at much less positive potentials due to the fast kinetics for chloride anion oxidation.

Hygroscopicity of secondary marine organic aerosols: Mixtures of alkylammonium salts and inorganic components

Field studies have identified alkylammonium salts as important components of secondary marine organic aerosols. In this work, we study the hygroscopic behavior of laboratory-generated alkylammonium aerosol particles, including monomethylammonium chloride (MMACl), dimethylammonium chloride (DMACl), trimethylammonium chloride (TMACl), diethylammonium chloride (DEACl), and their mixtures with inorganic salts containing ammonium sulfate (NH4)2SO4, sodium chloride NaCl, calcium nitrate Ca(NO3)2 and sodium sulfate Na2SO4 at different dry mass ratios with a hygroscopicity tandem differential mobility analyzer (HTDMA). The hygroscopic growth of pure alkylammonium salt particles (except for DEACl) reveals gradual water uptake over the whole studied range of relative humidities (RHs). In general, the impact of the presence of alkylammonium chloride on the phase behavior and hygroscopic growth of mixtures depends on the chemical composition of particles and volume fraction of the alkylammonium chloride in the mixtures. For alkylammonium/(NH4)2SO4 mixed particles (except for TMACl/(NH4)2SO4), the hygroscopic growth shows a smooth growth tendency when the organic content is high, while the deliquescence transition is observed for alkylammonium salt/NaCl mixtures at all mass ratios. Regarding the different mixtures of alkylammonium/Ca(NO3)2 particles, continuous water uptake without phase transition is observed over the studied RH range, indicating that alkylammonium salts impose no effect on the liquid-like state of calcium nitrate. The alkylammonium/Na2SO4 mixtures show obvious particle shrinkage prior to the deliquescence point. A similar behavior is also observed for alkylammonium salt/NaCl mixtures. The observed diameter reduction can be attributed to the transformation of porous or irregularly shaped solid particles into more compact near-spherical particles. In the following, measured growth factors (GFs) are compared with values predicted with the Zdanovskii–Stokes–Robinson (ZSR) mixing rule and ideal solution model. The ZSR predictions for different alkylammonium/inorganic mixtures are similar to the measured GFs as long as the mixed particles are in a liquid-like state.

Acid-Base Mediated Ligand Exchange on Near-Infrared Absorbing, Indium-Based III-V Colloidal Quantum Dots.

Colloidal quantum dots (QDs) made from In-based III-V semiconductors are emerging as a printable infrared material. However, the formulation of infrared inks and the formation of electrically conductive QD coatings is hampered by a limited understanding of the surface chemistry of In-based QDs. In this work, we present a case study on the surface termination of IR active III-V QDs absorbing at 1220 nm that were synthesized by reducing a mixture of indium halides and an aminoarsine by an aminophosphine in oleylamine. We find that this recently established synthesis method yields In(As,P) QDs with minor phosphorus admixing and a surface terminated by a mixture of oleylamine and chloride. Exposing these QDs to protic surface-active compounds RXH, such as fatty acids or alkanethiols, initiates a ligand exchange reaction involving the binding of the conjugate base RX- and the desorption of 1 equiv of alkylammonium chloride. Using density functional theory simulations, we confirm that the formation of the alkylammonium chloride salt can provide the energy needed to drive such acid/base mediated ligand exchange reactions, even for weak organic acids such as alkanethiols. We conclude that the unique surface termination of In(As,P) QDs, consisting of a mixture of L-type and X-type ligands and acid/base mediated ligand exchange, can form a general model for In-based III-V QDs synthesized using indium halides and aminopnictogens.

Effects of loblolly pine extract, primary and quaternary alkyl ammonium chlorides combined with burgundy oil from eastern red cedar against subterranean termites and wood-decay fungi

Burgundy oil (BO) from Eastern red cedar provides resistance against termites and wood-decay fungi and is enhanced when combined with an amylose inclusion complex (AIC) containing hexadecylammonium chloride (HAC). Indirect evidence also indicated that a methanol Loblolly pine extract (LPE) was inhibitory against termites. This study compared the effects of HAC and didecyldimethylammonium chloride (DDAC) combined with LPE and BO on termites and wood-decay fungi. Southern pine was treated by vacuum/pressure impregnation and resistance evaluated after exposure to termites and decay fungi. The combination of BO and either HAC/AIC or DDAC/AIC reduced wood mass losses by termites, increased termite mortality, and inhibited all wood-decay fungi. The HAC/AIC and DDAC/AIC resulted in equivalent mass losses by termites and termite mortalities. The DDAC was slightly more inhibitory than the HAC against wood-decay fungi. Given the slight advantage of DDAC over HAC and because DDAC is currently used to preserve wood, DDAC might be preferred over HAC. The LPE had a very minor effect on mass loss by termites, termite mortality, and only a slight inhibitory effect on G. trabeum and T. versicolor, while R. placenta and I. lacteus were unaffected. Higher concentrations of DDAC and/or LPE might improve protection against termites and wood-decay fungi.

Improved Access to Organo-Soluble Di- and Tetrafluoridochlorate(I)/(III) Salts.

A facile one‐pot gram‐scale synthesis of tetraalkylammonium tetrafluoridochlorate(III) [cat][ClF4] ([cat]=[NEt3Me]+, [NEt4]+) is described. An acetonitrile solution of the corresponding alkylammonium chloride salt is fluorinated with diluted fluorine at low temperatures. The reaction proceeds via the [ClF2]− anion which is structurally characterized for the first time. The potential application of [ClF4]− salts as fluorinating agents is evaluated by the reaction with diphenyl disulfide, Ph2S2, to pentafluorosulfanyl benzene, PhSF5. The CN moieties in acetonitrile and [B(CN)4]− are transferred in CF3 groups. Exposure of carbon monoxide, CO, leads to the formation of carbonyl fluoride, COF2, and elemental gold is dissolved under the formation of tetrafluoridoaurate [AuF4]−.

Homologous mixed micellar systems with non-ideal and asymmetric thermodynamic behavior

Mixtures of different kinds of homologous surfactants (potassium soaps, alkyltrimethylammonium bromides, alkylammonium chlorides, alkylsulfinyl ethanols and tritons) have been studied contemplating the peculiarities of each case. Two aggregation behaviors at low total molar fractions of the more hydrophilic surfactant at the mixture CMC have been identified: one-step micellization with mixed micelles with a relative large proportion of the more hydrophilic surfactant in the mixed micelles, and two-steps micellization with micelles with a very low proportion of the more hydrophilic surfactant, i.e. pure or almost pure micelles of the more hydrophobic component. A recently developed procedure for the thermodynamic analysis, the Equation Oriented Mixed Micellization Model (EOMMM) has been employed evidencing that these systems are not only non-ideal but also asymmetric.

Method combining BAC film and positive staining for the characterization of DNA intermediates by dark-field electron microscopy

DNA intermediate structures are formed in all major pathways of DNA metabolism. Transmission electron microscopy (TEM) is a tool of choice to study their choreography and has led to major advances in the understanding of these mechanisms, particularly those of homologous recombination (HR) and replication. In this article, we describe specific TEM procedures dedicated to the structural characterization of DNA intermediates formed during these processes. These particular DNA species contain single-stranded DNA regions and/or branched structures, which require controlling both the DNA molecules spreading and their staining for subsequent visualization using dark-field imaging mode. Combining BAC (benzyl dimethyl alkyl ammonium chloride) film hyperphase with positive staining and dark-field TEM allows characterizing synthetic DNA substrates, joint molecules formed during not only in vitro assays mimicking HR, but also in vivo DNA intermediates.

In Situ 2D Perovskite Formation and the Impact of the 2D/3D Structures on Performance and Stability of Perovskite Solar Cells

In article no. 1900199, Ana F. Nogueira and co-workers modify perovskite surfaces with alkylammonium chloride, which increases the stability of the solar cells, making it last longer when exposed to environmental conditions. After the modification, 2D/3D structures are formed and their chemical structures are identified. This mixture makes the films more humidity tolerant.

In Situ 2D Perovskite Formation and the Impact of the 2D/3D Structures on Performance and Stability of Perovskite Solar Cells

Hybrid organic and inorganic perovskite solar cells lack long‐term stability, and this negatively impacts the widespread application of this emerging and promising photovoltaic technology. Herein, aiming to increase the stability of perovskite films based on CH3NH3PbI3 and to deeply understand the formation of 2D structures, solutions of alkylammonium chlorides containing 8, 10, and 12 carbons are introduced during the spin‐coating on the surface of 3D perovskite films leading to the in situ formation of 2D structures. It is possible to identify the chemical formulae of some 2D structures formed by X‐ray diffraction and UV–vis analysis of the modified films. Interestingly, the increase in the stability of the CH3NH3PbI3 films due to the formation of a 2D + 3D perovskite network is only possible in planar TiO2 substrates. The increase in stability of the CH3NH3PbI3 films follows the surfactant molecule order: octylammonium (8C) > decylammonium (1 °C) > dodecylammonium (12C) chlorides > standard. An increase of 17.6% in the lifetime of the devices assembled with octylammonium‐modified perovskite film is observed compared with that of the standard device, which is directly linked to the improvement of the charge carrier lifetimes obtained from time‐correlated single photon counting measurements.

In situ generated amine as a Lewis base catalyst in the reaction of 3,7‐dinitro‐1,3,5,7‐tetraazabicyclo[3.3.1]nonane in nitric acid: Experimental and DFT study

AbstractThe problem how ammonium nitrate affects the nitrolysis of 3,7‐dinitro‐1,3,5,7‐tetraazabicyclo[3.3.1]nonane (DPT) in nitric acid to prepare 1,3,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) has puzzled chemists for decades. In this paper, experimental work and theoretical calculation are described to investigate the long‐standing challenge. The experiment results showed that ammonium nitrate or alkylammonium chlorides were in favor of the formation of 1‐nitroso‐3,5,7‐trinitro‐1,3,5,7‐tetraazacyclooctane (MNX) but hindered the conversion of MNX to HMX. A plausible catalytic mechanism was proposed. In which ammonia or amines, in situ generated from the unfavorable balance with their salts, act as Lewis base catalysts. At the same time, the DFT computation results reveal that rigid bicyclic transition states established with 1‐hydroxymethyl‐3,5,7‐trinitro‐1,3,5,7‐tetraazacyclooctane, ammonia (or amines) and three water molecules lead to very low activation energies. Then, a novel process for the preparation of MNX with excellent yield up to 78.5% was developed, which is free of the use of NaNO2 or N2O4 as nitroso resources.