title: Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters.
abstract: The sensitivity, or insensitivity, of catalysed reactions to catalyst structure is a commonly employed fundamental concept. Here we report on the nature of nano-catalysed ethylene hydrogenation, investigated through experiments on size-selected Ptn (n=8-15) clusters soft-landed on magnesia and first-principles simulations, yielding benchmark information about the validity of structure sensitivity/insensitivity at the bottom of the catalyst size range. Both ethylene-hydrogenation-to-ethane and the parallel hydrogenation-dehydrogenation ethylidyne-producing route are considered, uncovering that at the <1 nm size-scale the reaction exhibits characteristics consistent with structure sensitivity, in contrast to structure insensitivity found for larger particles. The onset of catalysed hydrogenation occurs for Ptn (n ≥ 10) clusters at T>150 K, with maximum room temperature reactivity observed for Pt13. Structure insensitivity, inherent for specific cluster sizes, is induced in the more active Pt13 by a temperature increase up to 400 K leading to ethylidyne formation. Control of sub-nanometre particle size may be used for tuning catalysed hydrogenation activity and selectivity.
authors.affiliation: Chair of Physical Chemistry, Catalysis Research Center, Chemistry Department, Technische Universität München, Lichtenbergstraße 4, Garching 85748, Germany.
authors.forename: Andrew S
authors.initials: AS
authors.lastname: Crampton
authors.affiliation: Chair of Physical Chemistry, Catalysis Research Center, Chemistry Department, Technische Universität München, Lichtenbergstraße 4, Garching 85748, Germany.
authors.forename: Marian D
authors.initials: MD
authors.lastname: Rötzer
authors.affiliation: Chair of Physical Chemistry, Catalysis Research Center, Chemistry Department, Technische Universität München, Lichtenbergstraße 4, Garching 85748, Germany.|Air Force Research Laboratory, Energetic Materials Branch, 2306 Perimeter Road, Eglin AFB, Florida 32542, USA.
authors.forename: Claron J
authors.initials: CJ
authors.lastname: Ridge
authors.affiliation: Chair of Physical Chemistry, Catalysis Research Center, Chemistry Department, Technische Universität München, Lichtenbergstraße 4, Garching 85748, Germany.
authors.forename: Florian F
authors.identifier: http://orcid.org/0000-0003-4369-6768
authors.initials: FF
authors.lastname: Schweinberger
authors.affiliation: Chair of Physical Chemistry, Catalysis Research Center, Chemistry Department, Technische Universität München, Lichtenbergstraße 4, Garching 85748, Germany.
authors.forename: Ueli
authors.initials: U
authors.lastname: Heiz
authors.affiliation: School of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332-0430, USA.
authors.forename: Bokwon
authors.initials: B
authors.lastname: Yoon
authors.affiliation: School of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332-0430, USA.
authors.forename: Uzi
authors.initials: U
authors.lastname: Landman
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