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Proton transfer is a key step of the lithium-mediated electrochemical reduction of nitrogen to ammonia. Herein, we investigate the impact of the chemical nature of the proton carrier on the performance and highlight shuttles that enable effective ammonia synthesis.

Thermal energy storage systems utilising phase change materials have the potential to overcome the intermittency issues associated with most renewable energy sources, significantly contributing to the decarbonisation of the energy sector. While the concept of storing energy in the latent heat of a phase transition is not new, large scale systems employing this concept have not yet realised their full potential. This is in large part due to the shortcomings of conventionally used materials – whether it be issues with their flammability, chemical and thermal instability, corrosivity, poor cycling stability, or a combination of these. Ionic liquids offer a suite of inherent “green” properties that translate well into the field of phase change materials, namely low volatility, low flammability, and good thermal and chemical stability, alongside the potential to tune their chemical and phase properties. In this Perspective, we discuss the evolution and promise of the emerging field of ionic liquids for renewable thermal energy storage. Systems are considered from a holistic, sustainable point of view, demonstrating the importance of assessing material origins and synthetic pathways as well as system performance through lifecycle assessment. We elucidate the emerging design rules for optimising thermal properties, and in doing so attempt to provide an overview of promising emerging systems and future directions.

Shuttling protons in ammonia synthesis An electrochemical route to ammonia could substantially lower the greenhouse gas emissions associated with the current thermal Haber-Bosch process. One relatively promising option under study involves reductive formation of lithium nitride, which can be protonated to ammonia. However, the ethanol used to date as a local proton source in these studies may degrade under the reaction conditions. Suryanto et al. report the use of a tetraalkyl phosphonium salt in place of ethanol (see the Perspective by Westhead et al. ). This cation can stably undergo deprotonation–reprotonation cycles and, as an added benefit, it enhances the ionic conductivity of the medium. Science , abg2371, this issue p. 1187 ; see also abi8329, p. 1149

Charge transport properties in single-walled carbon nanotubes (SWCNTs) can be significantly modified through doping, tuning their electrical and thermoelectric properties. In our study, we used more than 40 nitrogen-bearing compounds as dopants and determined their impact on the material's electrical conductivity. The application of nitrogen compounds of diverse structures and electronic configurations enabled us to determine how the dopant nature affects the SWCNTs. The results reveal that the impact of these dopants can often be anticipated by considering their Hammett's constants and pKa values. Furthermore, the empirical observations supported by first-principles calculations indicate that the doping level can be tuned not only by changing the type and the concentration of dopants but also by varying the orientation of nitrogen compounds around SWCNTs.

As a result of strict regulations of phthalate plasticizers, alternative non-phthalate forms are desired and increasingly used. This work presents a synthetic method for alternative plasticizers (dialkyl succinates and adipates) via esterification of succinic and adipic acid with alcohols: butan-1-ol and 2-ethylhexan-1-ol. Ionic liquids were synthesized by the reaction of triethylamine with over-equimolar (1:2.7) amounts of sulfuric(VI) acid, which were used as an acidic catalyst and solvent. The two-phase liquid–liquid system was formed during the reaction due to immiscibility of the esters with the ionic liquid. This phenomenon is a driving force of this process, shifting the equilibrium toward the product formation. As a result, dialkyl succinates and adipates were obtained in high yields (99%) and selectivities (&gt, 99%), under mild reaction conditions at 70–80 °C and using a 4:1 molar ratio of alcohol to acid and 15 mol% of catalyst. The catalyst was recycled 10 times without any loss of activity. This alternative method is highly competitive: it involves a simple procedure for product isolation as well as a high yield and purity of the resulting esters. These advantages make this method sustainable and promising for industrial applications.

The sodium-ion battery (SIB) is proposed as a complementary technology to today's commercially dominant lithium-ion battery (LIB). While much know-how can be transferred from LIBs to SIBs, adjustments are still necessary, not the least for the electrolytes employed. Here the use of anion amphiprotic ionic liquid (AAIL) based electrolytes is proposed for SIB application. Two different AAILs, based on organic trifluoromethylsulfonylamide (TFSAm) and inorganic HSO4− anions, respectively, doped with NaTFSI salt have been studied, focusing on electrochemical stability and transport properties, complemented by studies of the ion–ion interactions, and final sodium-ion battery performance via stripping/plating vs. sodium metal electrodes.

The kinetics of polymerization of Bisphenol-A diglycidyl ether (DGEBA), a well-known epoxy resin, with two ionic amines 1-(3-aminopropyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide ([apbim][NTf2]) and the tetrabutylammonium leucine ([N4444][Leu]) have been studied with the use of differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS) at various temperatures. We found many fundamental differences between the progress of this reaction with respect to the classical system (curing of epoxy resin with ordinary nonconducting hardeners). One of the most significant differences is related to the mechanism of polymerization. It is worthwhile to mention that usually the autocatalytic model is used to describe the curing of DGEBA with ordinary amines. However, herein, the kinetic curves followed a clearly exponential shape characteristic of first-order kinetics. We claim that the change in mechanism of polymerization is related to the presence of a conducting amine that acts as...

A new method for the rapid synthesis of lactones via the one-pot oxidation of alcohols with potassium peroxymonosulphate in an ionic liquid was developed. The use of microwave or ultrasonic irradiation increased the reaction rates significantly. Additionally, new peroxymonosulphate ionic liquids were synthesised and used as effective oxidants in the synthesis of lactones.

The synthesis and characterisation of new hydrogen-bond-rich ionic liquids and studies of their catalytic performance in Diels–Alder reactions are described. D-Glucose and chloroalcohols were used as the raw materials and as the sources of hydroxyl groups for the synthesis of ionic-liquid cations, whereas weakly coordinating bis(trifluoromethylsulfonyl)imide was used as the anion. The new ionic liquids were analysed by 1H and 13C NMR spectroscopy and by ESI-MS experiments, which confirmed their structures. In addition, the thermal data of the studied ionic liquids measured by differential scanning calorimetry and thermogravimetric analysis showed that these compounds tend to form a glass at temperatures in the range of −29 °C to −16 °C and are thermally stable from ambient temperature to at least 430 °C, most likely because of the presence of bis(trifluoromethylsulfonyl)imide anions. The performance of the ionic liquids in the model reaction of cyclopentadiene with diethyl maleate or methyl acrylate was investigated. The studied ionic liquids showed high activity even when present in catalytic amounts (4 mol% with respect to the dienophile). An increase in the number of hydroxyl groups present in the ionic liquid structure resulted in higher reaction rates.