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Issue 38, 2014
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Solvation and stabilization of palladium nanoparticles in phosphonium-based ionic liquids: a combined infrared spectroscopic and density functional theory study

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Abstract

Analysis of infrared spectra of palladium nanoparticles (NPs) immersed in the tri-tert-butyl-R-phosphonium-based ionic liquids (ILs) demonstrates that both cations and anions of the ILs interact with the NPs. According to quantum-chemical simulations of these interactions, the binding energy of anions to the Pd6 cluster, taken as a minimal-size model of the NPs, increases from ∼6 to ∼27 kcal mol−1 in the order [PF6] ≈ [BF4] < [Tf2N] < [OTf] < [Br] ≪ [TFA]. In contrast, the binding energy for all types of the [But3PR]+ cations slightly varies at about ∼22 kcal mol−1 only moderately depending on the choice of the R moiety (n-pentyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxy-2-oxoethyl). As a result, the energies of interaction between a Pd6 cluster and various ion pairs, formed by the abovementioned counter-ions, follow the order found for the anions and vary from ∼24 to ∼47 kcal mol−1. These values are smaller than the energy of addition of a Pd atom to a Pdn cluster (∼58 kcal mol−1), which suggests kinetic stabilization of the NPs in phosphonium-based ILs rather than thermodynamic stabilization. The results are qualitatively similar to the trends found earlier for interactions between palladium clusters and components of imidazolium-based ILs, in spite of much larger contributions of the London dispersion forces to the binding of the [But3PR]+ cations to the cluster (up to 80%) relative to the case of 1-R-3-methylimidazolium cations (up to 40%).

Graphical abstract: Solvation and stabilization of palladium nanoparticles in phosphonium-based ionic liquids: a combined infrared spectroscopic and density functional theory study

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The article was received on 10 Jun 2014, accepted on 12 Aug 2014 and first published on 27 Aug 2014


Article type: Paper
DOI: 10.1039/C4CP02547D
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Citation: Phys. Chem. Chem. Phys., 2014,16, 20672-20680

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    Solvation and stabilization of palladium nanoparticles in phosphonium-based ionic liquids: a combined infrared spectroscopic and density functional theory study

    E. E. Zvereva, S. Grimme, S. A. Katsyuba, V. V. Ermolaev, D. A. Arkhipova, N. Yan, V. A. Miluykov, O. G. Sinyashin and A. Aleksandrov, Phys. Chem. Chem. Phys., 2014, 16, 20672
    DOI: 10.1039/C4CP02547D

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