Aggregation control of Ru and Ir nanoparticles by tunable aryl alkyl imidazolium ionic liquids

Abstract

Metal-nanoparticles (M-NPs) were synthesized in a wet-chemical synthesis route in tunable aryl alkyl ionic liquids (TAAILs) based on the 1-aryl-3-alkyl-substituted imidazolium motif from Ru₃(CO)₁₂ and Ir₄(CO)₁₂ by microwave-heating induced thermal decomposition. The size and size dispersion of the NPs were determined by transmission electron microscopy (TEM) to an average diameter of 2.2(±0.1) to 3.9(±0.3) nm for Ru-NPs and to an average diameter of 1.4(±0.1) to 2.4(±0.1) nm for Ir-NPs. The TAAILs used contain the same bis(trifluoromethylsulfonyl)imide anion but differ in the substituents on the 1-aryl ring, e.g. 2-methyl-, 4-methoxy- and 2,4-dimethyl groups and in the 3-alkyl chain lengths (C₄H₉, C₅H₁₁, C₈H₁₇, C₉H₁₉, C₁₁H₂₃). All used TAAILs are suitable for the stabilization of Ru- and Ir-NPs over months in the IL dispersion. Different from all other investigations on M-NP/IL systems which we are aware of the particle separation properties of the TAAILs vary strongly as a function of the aryl substituent. Good NP separation can be achieved with the 4-methoxyphenyl- and 2,4-dimethylphenyl-substituted ILs, irrespective of the 3-alkyl chain lengths. Significant aggregation can be observed for 2-methylphenyl-substituted ILs. The good NP separation can be correlated with a negative electrostatic potential at the 4-methoxyphenyl or 4-methylphenyl substituent that is in the para-position of the aryl ring, whereas the 2-(ortho-)methylphenyl group assumes no negative potential. ε-ePC-SAFT calculations were used to validate that the interactions between ILs and the washing agents (required for TEM analyses) do not cause the observed aggregation/separation behaviour of the M-NPs. Ru-NPs were investigated as catalysts for the solvent-free hydrogenation of benzene to cyclohexane under mild conditions (70 °C, 10 bar) with activities up to 760 (mol cyclohexane) (mol Ru)⁻¹ h⁻¹ and over 95% conversion in ten consecutive runs for Ru-NPs. No significant loss of catalytic activity could be observed.