Influence of alcohols on the inter-ion interactions in ionic liquids: A molecular dynamics study

Figueiredo, Nádia M.; Voroshylova, Iuliia V.; Koverga, Volodymyr; Ferreira, Elisabete S.C.; Cordeiro, M. Natália D. S.

doi:10.1016/j.molliq.2019.111538

Cited by 14 publications

(14 citation statements)

References 111 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“… 34 − 36 Nonetheless, the physicochemical properties of ILs can be customized and optimized for instance by addition of cosolvents, such as water or alcohols, in order to obtain the desired characteristics for each purpose. 37 − 40 Among the huge number of possible IL/cosolvent mixtures, the combination of ethyl ammonium nitrate (EAN) and methanol (MeOH) represents a very interesting system both from an academic and applicative point of view. EAN, whose structural formula is shown in Figure 1 , is indeed one of the most widely investigated protic ionic liquid (PIL), which is prepared by a proton transfer reaction and it is thus characterized by proton-donor and proton-acceptor sites.…”

Section: Introductionmentioning

confidence: 99%

On the Coordination Chemistry of the lanthanum(III) Nitrate Salt in EAN/MeOH Mixtures

et al. 2021

View full text Add to dashboard Cite

A thorough structural characterization of the La(NO 3 ) 3 salt dissolved into several mixtures of ethyl ammonium nitrate (EAN) and methanol (MeOH) with EAN molar fraction χ EAN ranging from 0 to 1 has been carried out by combining molecular dynamics (MD) and X-ray absorption spectroscopy (XAS). The XAS and MD results show that changes take place in the La 3+ first solvation shell when moving from pure MeOH to pure EAN. With increasing the ionic liquid content of the mixture, the La 3+ first-shell complex progressively loses MeOH molecules to accommodate more and more nitrate anions. Except in pure EAN, the La 3+ ion is always able to coordinate both MeOH and nitrate anions, with a ratio between the two ligands that changes continuously in the entire concentration range. When moving from pure MeOH to pure EAN, the La 3+ first solvation shell passes from a 10-fold bicapped square antiprism geometry where all the nitrate anions act only as monodentate ligands to a 12-coordinated icosahedral structure in pure EAN where the nitrate anions bind the La 3+ cation both in mono- and bidentate modes. The La 3+ solvation structure formed in the MeOH/EAN mixtures shows a great adaptability to changes in the composition, allowing the system to reach the ideal compromise among all of the different interactions that take place into it.

show abstract

Section: Introductionmentioning

confidence: 99%

On the Coordination Chemistry of the lanthanum(III) Nitrate Salt in EAN/MeOH Mixtures

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Regarding the charge of the anion, one can see that it shows an increase of its negative value according to the Mülliken population analysis (see Table S2 , ESI), opposite to the general behaviour. That can be attributed to the basis set dependence of this scheme, which can indeed produce this type of results [ 4 ]. Still, the Natural Population Analysis (NPA) shows a small reduction of the charge in the anion when one cation is present but a higher decrease when there are two of them, showing thus the importance of the charge for the stabilisation of [Bmim] 2 [SnCl 4 ].…”

Section: Resultsmentioning

confidence: 99%

“…These compounds have unique properties, such as negligible volatilities, high thermal and electrochemical stabilities, reasonable ionic and viscosity characteristics, wide electrochemical windows and tuneable solvation properties [ 2 ]. Moreover, ILs can be fine-tuned by changing their cation or anion structure or by adding other solvents, such as water or alcohols [ 1 , 3 , 4 , 5 ].…”

Section: Introductionmentioning

confidence: 99%

Unravelling the Interactions of Magnetic Ionic Liquids by Energy Decomposition Schemes: Towards a Transferable Polarizable Force Field

2021

Self Cite

View full text Add to dashboard Cite

This work aims at unravelling the interactions in magnetic ionic liquids (MILs) by applying Symmetry-Adapted Perturbation Theory (SAPT) calculations, as well as based on those to set-up a polarisable force field model for these liquids. The targeted MILs comprise two different cations, namely: 1-butyl-3-methylimidazolium ([Bmim]+) and 1-ethyl-3-methylimidazolium ([Emim]+), along with several metal halides anions such as [FeCl4]−, [FeBr4]−, [ZnCl3]− and [SnCl4]2− To begin with, DFT geometry optimisations of such MILs were performed, which in turn revealed that the metallic anions prefer to stay close to the region of the carbon atom between the nitrogen atoms in the imidazolium fragment. Then, a SAPT study was carried out to find the optimal separation of the monomers and the different contributions for their interaction energy. It was found that the main contribution to the interaction energy is the electrostatic interaction component, followed by the dispersion one in most of the cases. The SAPT results were compared with those obtained by employing the local energy decomposition scheme based on the DLPNO-CCSD(T) method, the latter showing slightly lower values for the interaction energy as well as an increase of the distance between the minima centres of mass. Finally, the calculated SAPT interaction energies were found to correlate well with the melting points experimentally measured for these MILs.

show abstract

“…Self-diffusion coefficients were only evaluated after examining the attainment of a diffusive regime. To accomplish this, the parameter β was computed for each species and each simulation cell, as comprehensively described elsewhere [ 58 , 59 , 60 , 61 ]. The GRACE software was used for the numerical integration of RDFs for coordination numbers (CNs) assessment.…”

Section: Methodsmentioning

confidence: 99%

Computational Modelling and Sustainable Synthesis of a Highly Selective Electrochemical MIP-Based Sensor for Citalopram Detection

et al. 2022

Self Cite

View full text Add to dashboard Cite

A novel molecularly imprinted polymer (MIP) has been developed based on a simple and sustainable strategy for the selective determination of citalopram (CTL) using screen-printed carbon electrodes (SPCEs). The MIP layer was prepared by electrochemical in situ polymerization of the 3-amino-4 hydroxybenzoic acid (AHBA) functional monomer and CTL as a template molecule. To simulate the polymerization mixture and predict the most suitable ratio between the template and functional monomer, computational studies, namely molecular dynamics (MD) simulations, were carried out. During the experimental preparation process, essential parameters controlling the performance of the MIP sensor, including CTL:AHBA concentration, number of polymerization cycles, and square wave voltammetry (SWV) frequency were investigated and optimized. The electrochemical characteristics of the prepared MIP sensor were evaluated by both cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. Based on the optimal conditions, a linear electrochemical response of the sensor was obtained by SWV measurements from 0.1 to 1.25 µmol L−1 with a limit of detection (LOD) of 0.162 µmol L−1 (S/N = 3). Moreover, the MIP sensor revealed excellent CTL selectivity against very close analogues, as well as high imprinting factor of 22. Its applicability in spiked river water samples demonstrated its potential for adequate monitoring of CTL. This sensor offers a facile strategy to achieve portability while expressing a willingness to care for the environment.

show abstract

Influence of alcohols on the inter-ion interactions in ionic liquids: A molecular dynamics study

Cited by 14 publications

References 111 publications

On the Coordination Chemistry of the lanthanum(III) Nitrate Salt in EAN/MeOH Mixtures

On the Coordination Chemistry of the lanthanum(III) Nitrate Salt in EAN/MeOH Mixtures

Unravelling the Interactions of Magnetic Ionic Liquids by Energy Decomposition Schemes: Towards a Transferable Polarizable Force Field

Computational Modelling and Sustainable Synthesis of a Highly Selective Electrochemical MIP-Based Sensor for Citalopram Detection

Contact Info

Product

Resources

About