Design of Highly Selective Platinum Nanoparticle Catalysts for the Aerobic Oxidation of KA‐Oil using Continuous‐Flow Chemistry. Issue 5 (2nd February 2016)

• Record Type: Journal Article
• Authors: Gill, Arran M.; Hinde, Christopher S.; Leary, Rowan K.; Potter, Matthew E.; Jouve, Andrea; Wells, Peter P.; Midgley, Paul A.; Thomas, John M.; Raja, Robert
• Is Part Of: ChemSusChem. Volume 9:Issue 5(2016:Mar.)
• Page Start: 423
• Page End: 427
• Publication Date: 2016-02-02
• Subjects: aerobic oxidation -- flow chemistry -- heterogeneous catalysis -- nanoparticles -- selectivity; Green chemistry -- Periodicals; Sustainable engineering -- Periodicals; Chemistry -- Periodicals; Chemical engineering -- Periodicals; 660
• DOI: 10.1002/cssc.201501264
• Languages: English
• ISSNs: 1864-5631

Abstract

Abstract: Highly active and selective aerobic oxidation of KA‐oil to cyclohexanone (precursor for adipic acid and ɛ‐caprolactam) has been achieved in high yields using continuous‐flow chemistry by utilizing uncapped noble‐metal (Au, Pt & Pd) nanoparticle catalysts. These are prepared using a one‐step in situ methodology, within three‐dimensional porous molecular architectures, to afford robust heterogeneous catalysts. Detailed spectroscopic characterization of the nature of the active sites at the molecular level, coupled with aberration‐corrected scanning transmission electron microscopy, reveals that the synthetic methodology and associated activation procedures play a vital role in regulating the morphology, shape and size of the metal nanoparticles. These active centers have a profound influence on the activation of molecular oxygen for selective catalytic oxidations. Abstract : Revealed: Isolation by activation ! Platinum, palladium and gold nanoparticles are generated in situ by anion extrusion from porous framework architectures. Spectroscopic and aberration‐corrected scanning transmission electron microscopy reveal that activation conditions are crucial for the generation of isolated active centers. The design strategy affords highly active and selective catalysts for the industrially significant aerobic oxidation of KA‐oil under continuous‐flow conditions.