In Situ Formed “Weakly Ligated/Labile Ligand” Iridium(0) Nanoparticles and Aggregates as Catalysts for the Complete Hydrogenation of Neat Benzene at Room Temperature and Mild Pressures

• Published in: Langmuir 2010-07, Vol.26 (14), p.12455-12464
• Main Authors: Bayram, Ercan, Zahmakıran, Mehmet, Özkar, Saim, Finke, Richard G
• Format: Article
• Language: English
• Subjects: Devices and Applications: Sensors, Fluidics, Patterning, Catalysis, Photonic Crystals
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/la101390e

“Weakly ligated/labile ligand” nanoparticles, that is nanoparticles where only weakly coordinated ligands plus the desired catalytic reactants are present, are of fundamental interest. Described herein is a catalyst system for benzene hydrogenation to cyclohexane consisting of “weakly ligated/labile ligand” Ir(0) nanoparticles and aggregates plus dry-HCl formed in situ from commercially available [(1,5-COD)IrCl]2 plus 40 ± 1 psig (∼2.7 atm) H2 at 22 ± 0.1 °C. Multiple control and other experiments reveal the following points: (i) that this catalyst system is quite active with a TOF (turnover frequency) of 25 h−1 and TTO (total turnovers) of 5250; (ii) that the BF4 − and PF6 − iridium salt precursors, [(1,5-COD)Ir(CH3CN)2]BF4 and [(1,5-COD)Ir(CH3CN)2]PF6, yield inferior catalysts; (iii) that iridium black with or without added, preformed HCl cannot achieve the TOF of 25 h−1 of the in situ formed Ir(0)/dry-HCl catalyst. However and importantly, CS2 poisoning experiments yield the same activity per active iridium atom for both the Ir(0)/dry-HCl and Ir black/no-HCl catalysts (12.5 h−1 Ir1−), but reveal that the Ir(0)/dry-HCl system is 10-fold more dispersed compared to the Ir(0) black catalyst. The simple but important and key result is that “weakly ligated/labile ligand” Ir(0) nanoparticles and aggregates have been made in situ as demonstrated by the fact that they have identical, per exposed Ir(0) activity within experimental error to Ir(0) black and that they have no possible ligands other than those desired for the catalysis (benzene and H2) plus the at best poor ligand HCl. As expected, the in situ catalyst is poorly stabilized, exhibiting only 60% of its initial activity in a second run of benzene hydrogenation and resulting in bulk metal precipitation. However, stabilization of the Ir(0) nanoparticles with a ca. 2-fold higher catalytic activity and somewhat longer lifetime for the complete hydrogenation of benzene was accomplished by supporting the Ir(0) nanoparticles onto zeolite-Y (TOF of 47 h−1 and 8600 TTO under otherwise identical conditions). Also reported is the interesting result that Cl− (present as Proton Sponge·H+Cl−) completely poisons benzene hydrogenation catalysis, but not the easier cyclohexene hydrogenation catalysis under otherwise the same conditions, results that suggest different active sites for these ostensibly related hydrogenation reaction. The results suggest that synthetic routes to “weakly ligated/labile ligand” nanoparticles