Adsorption Behavior of the 1,3-Dimethylimidazolium Thiocyanate and Tetracyanoborate Ionic Liquids at Anatase (101) Surface

Weber, Henry; Bredow, Thomas; Kirchner, Barbara

doi:10.1021/acs.jpcc.5b02347

Cited by 22 publications

(40 citation statements)

References 110 publications

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“…In the latter case, an acidic hydrogen atom is replaced by a methyl group, which disables an important H−O interaction. This interaction pattern was found to be significant for imidazolium adsorption on TiO 2 . However, the magnitude of the deviation of Δ E L from the alkylimidazolium cation is still comparably small.…”

Section: Resultsmentioning

confidence: 89%

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Ionic Liquid Induced Band Shift of Titanium Dioxide

Weber

Kirchner

2016

ChemSusChem

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Ionic liquids (ILs) have become an established option for the use as electrolytes in dye-sensitized solar cells. In the present study, the adsorption of a multitude of different ILs on a TiO2 surface is studied systematically, focusing on the energetic modifications of the semiconductor. The cation was found to generally cause an energetic downward shift of the TiO2 band levels by accepting electron density from the surface, and the anions were observed to function in the opposite direction, raising the energy levels by donating electron density. Both effects counterbalance each other, leaving the desired outcome dependent on the choice of the specific IL, i.e., the choice of the cation/anion combination. The correlation of the band levels with the properties of the IL was successfully achieved. The dipole moment of the adsorbed ionic liquid species showed little to no correlation with the semiconductor energetics, but the charge transfer calculated by radical Voronoi tessellation revealed a high correlation. The current findings contribute to a deeper understanding of the role of the electrolyte in dye-sensitized solar cells, and ILs in general, and help with choosing and tuning of the electrolyte solutions in existing applications.

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Section: Resultsmentioning

confidence: 89%

“…This cation was chosen because it is widely used among different ionic liquids. Moreover, we previously studied this cation in the context of TiO 2 adsorption . Consequently, different cations were investigated by keeping iodide as the anion constant.…”

Section: Resultsmentioning

confidence: 99%

Ionic Liquid Induced Band Shift of Titanium Dioxide

Weber

Kirchner

2016

ChemSusChem

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“…48 Indeed, PBE and RPBE in conjunction with D3 or D3BJ correction is a focus to our attention as has been successfully used computational levels for the treatment of complex molecular adlayers on inorganic surfaces. [49][50][51][52] Note by passing by that only twobody terms were considered, known to play a main role in finite systems, although three-body terms become important for some thermochemical properties already in finite systems. 47 In addition, we also consider the more physically grounded many body dispersion (MBD) method of Tkatchenko and coworkers.…”

Section: Computational Detailsmentioning

confidence: 99%

Adding Pieces to the CO/Pt(111) Puzzle: The Role of Dispersion

et al. 2017

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The so called CO/Pt(111) puzzle, the experimentally proven preference of CO to adsorb on top site on Pt(111) surface versus the standard density functional theory (DFT) methods prediction for threefold hollow sites, was alleged to be solved by properly leveling CO frontier molecular orbitals. However, the subtle energy difference between top and hollow sites is of the same order of the possible contribution of dispersive forces on this interaction. Here, the role of dispersion on this system is investigated by considering the PBE, PBEsol, RevPBE, RPBE, and SOGGA11 generalized gradient approximation (GGA) based exchange correlation functionals, non-separable functionals such as N12, and the TPSS and M06-L meta-GGA type functionals together to D2, D3, D3BJ and MBD dispersion corrections. Results reinforce the advice of using M06-L for a correct description of CO adsorption site preference even if including dispersion leads to a change of site and a noticeable overestimation of the adsorption energy indicating the presence of error compensations effects. The present results also highlight that dispersion contributes in bridging the preference gap between top and hollow sites when other functionals are used. Dispersive forces play a role in site preference for CO on Pt(111) and it is likely that a similar situation is encountered on other late transition metals. Therefore, dispersion is to be considered to reach a complete unbiased description of CO adsorption on metals. Nevertheless, including dispersion leads to adsorption energy values which overestimate the experimental value indicating limitations of the existing, widely used, density functionals.

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“…Thus, although dispersion forces have been proved to influence dramatically the interaction between the ions within the ionic pair, common functionals as B3LYP, in which dispersion terms or procedures to correct SIE are not included, are being used currently for geometry optimization . Furthermore, this kind of calculations is also affected by the SIE …”

Section: Introductionmentioning

confidence: 99%

“…[26,28,29] Furthermore, this kind of calculations is also affected by the SIE. [30,31] In this work, the role of dispersion and the partial correction of SIE in the optimized geometry and the electron density has been elucidated. An evaluation of whether the effect of these errors depends on the ions that compose the ion pair or not by changing the anion and the cation has been carried out.…”

Section: Introductionmentioning

confidence: 99%

The role of errors related to DFT methods in calculations involving ion pairs of ionic liquids

et al. 2017

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Ionic liquids (ILs) play a key role in many chemical applications. As regards the theoretical approach, ILs show added difficulties in calculations due to the composition of the ion pair and to the fact that they are liquids. Although density functional theory (DFT) can treat this kind of systems to predict physico-chemical properties, common versions of these methods fail to perform accurate predictions of geometries, interaction energies, dipole moments, and other properties related to the molecular structure. In these cases, dispersion and self-interaction error (SIE) corrections need to be introduced to improve DFT calculations involving ILs. We show that the inclusion of dispersion is needed to obtain good geometries and accurate interaction energies. SIE needs to be corrected to describe the charges and dipoles in the ion pair correctly. The use of range-separated functionals allows us to obtain interaction energies close to the CCSD(T) level. © 2017 Wiley Periodicals, Inc.

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Adsorption Behavior of the 1,3-Dimethylimidazolium Thiocyanate and Tetracyanoborate Ionic Liquids at Anatase (101) Surface

Cited by 22 publications

References 110 publications

Ionic Liquid Induced Band Shift of Titanium Dioxide

Ionic Liquid Induced Band Shift of Titanium Dioxide

Adding Pieces to the CO/Pt(111) Puzzle: The Role of Dispersion

The role of errors related to DFT methods in calculations involving ion pairs of ionic liquids

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