Structural, electronic and catalytic properties of palladium nanoparticles supported on poly(ionic liquid)

Abstract

The structural, electronic and support effect on palladium nanoparticles (Pd NPs) prepared by sputtering deposition and chemical reduction of a Pd(II) precursor in/on a poly(ionic liquid) (PIL) was investigated in the selective hydrogenation of alpha,beta-unsaturated carbonyl compounds and dienes. Sputtering deposition generates naked NPs with a narrow size distribution (3.2-3.8 nm) that are predominantly composed of Pd(0) (85-100%). Conversely, chemical reduction produces PIL-covered NPs with almost twice the average size (6.6 nm) and only 15% Pd(0). Regard the catalytic performance, support composition (by ionic liquid (IL) addition or not) and NP location are decisive. The best activity and selectivity was obtained with imprinted Pd NPs on a PIL/IL mixture (D-MPIL.NTf2/IL-Pd catalyst). A kinetic investigation was conducted using 2-cyclohexen-1-one (CHN) and D-MPIL.NTf2/IL-Pd catalyst revealing that this reaction follows the Langmuir-Hinshelwood mechanism. Enthalpies obtaining from a Van't Hoff plot show that the adsorption of the CHN substrate on the surface of the PIL-Pd catalyst is an exothermic process (-9 kJ mol(-1)), whereas H-2 adsorption occurs by an endothermic process (12 kJ mol(-1)). This distinct behavior is consistent with the rate determining step proposed, in which the independent adsorption of reagents is followed by the hydrogenation of a pi-allyl intermediate on the catalyst surface.

The structural, electronic and support effect on palladium nanoparticles (Pd NPs) prepared by sputtering deposition and chemical reduction of a Pd(II) precursor in/on a poly(ionic liquid) (PIL) was investigated in the selective hydrogenation of alpha,beta-unsaturated carbonyl compounds and dienes. Sputtering deposition generates naked NPs with a narrow size distribution (3.2-3.8 nm) that are predominantly composed of Pd(0) (85-100%). Conversely, chemical reduction produces PIL-covered NPs with almost twice the average size (6.6 nm) and only 15% Pd(0). Regard the catalytic performance, support composition (by ionic liquid (IL) addition or not) and NP location are decisive. The best activity and selectivity was obtained with imprinted Pd NPs on a PIL/IL mixture (D-MPIL.NTf2/IL-Pd catalyst). A kinetic investigation was conducted using 2-cyclohexen-1-one (CHN) and D-MPIL.NTf2/IL-Pd catalyst revealing that this reaction follows the Langmuir-Hinshelwood mechanism. Enthalpies obtaining from a Van't Hoff plot show that the adsorption of the CHN substrate on the surface of the PIL-Pd catalyst is an exothermic process (-9 kJ mol(-1)), whereas H-2 adsorption occurs by an endothermic process (12 kJ mol(-1)). This distinct behavior is consistent with the rate determining step proposed, in which the independent adsorption of reagents is followed by the hydrogenation of a pi-allyl intermediate on the catalyst surface.