title: Surface activation of Pt nanoparticles synthesised by "hot injection" in the presence of oleylamine.
abstract: Oleylamine (OA) based "hot injection" colloidal synthesis offers a versatile approach to the synthesis of highly monodisperse metallic and multi-metallic alloyed nanostructures in the absence of potentially toxic and unstable phosphine compounds. For application in heterogeneous catalysis and electrocatalysis, the adsorbed OA species at the metal surfaces should be effectively removed without compromising the structure and composition of the nanostructures. Herein, we investigate the removal of OA from colloidal Pt nanoparticles through 1) "chemical methods" such as washing in acetic acid or ethanol, and ligand exchange with pyridine; and 2) thermal pre-treatment between 185 and 400 °C in air, H2 or Ar atmospheres. The electrochemical reactivity of Pt nanoparticles is acutely affected by the presence of surface organic impurities, making this material ideal for monitoring the effectiveness of OA removal. The results showed that thermal treatment in Ar at temperatures above 400 °C provides highly active particles, with reactivity comparable to the benchmark commercial catalyst, Pt/ETEK. The mechanism involved in thermal desorption of OA was also investigated by thermogravimetric analysis coupled to mass spectrometry (TGA-MS). Oxidation of HCOOH and adsorbed CO in acidic solution were used as test reactions to assess the Pt electrocatalytic activity.
authors.affiliation: School of Chemistry, University of Bristol, Cantocks Close, Bristol, BS8 1TS (UK), Fax: (+44) 117-927-7985.
authors.forename: Jo J L
authors.initials: JJ
authors.lastname: Humphrey
authors.affiliation: Sasol Technology UK Ltd. Purdie Building, North Haugh, St Andrews, Fife, Scotland, KY16 9ST (UK).
authors.forename: Sajanikumari
authors.initials: S
authors.lastname: Sadasivan
authors.affiliation: School of Chemistry, University of Bristol, Cantocks Close, Bristol, BS8 1TS (UK), Fax: (+44) 117-927-7985.
authors.forename: Daniela
authors.initials: D
authors.lastname: Plana
authors.affiliation: School of Chemistry, University of Bristol, Cantocks Close, Bristol, BS8 1TS (UK), Fax: (+44) 117-927-7985.
authors.forename: Verónica
authors.initials: V
authors.lastname: Celorrio
authors.affiliation: Sasol Technology UK Ltd. Purdie Building, North Haugh, St Andrews, Fife, Scotland, KY16 9ST (UK).
authors.forename: Robert A
authors.initials: RA
authors.lastname: Tooze
authors.affiliation: School of Chemistry, University of Bristol, Cantocks Close, Bristol, BS8 1TS (UK), Fax: (+44) 117-927-7985. david.fermin@bristol.ac.uk.
authors.forename: David J
authors.initials: DJ
authors.lastname: Fermín
keywords: electrocatalysis; nanoparticles; platinum; supported catalysts; surface activation