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    Chemisorption of CO and mechanism of CO oxidation on supported platinum nanoclusters

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    Type
    Article
    Authors
    Allian, Ayman Daoud
    Takanabe, Kazuhiro cc
    Fujdala, Kyle L.
    Hao, Xianghong
    Truex., Timothy J.
    Cai, Juan
    Buda, Corneliu
    Neurock, Matthew
    Iglesia, Enrique
    KAUST Department
    Biological and Environmental Sciences and Engineering (BESE) Division
    Physical Sciences and Engineering (PSE) Division
    Chemical Science Program
    KAUST Catalysis Center (KCC)
    Catalysis for Energy Conversion (CatEC)
    Date
    2011-03-30
    Permanent link to this record
    http://hdl.handle.net/10754/561737
    
    Metadata
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    Abstract
    Kinetic, isotopic, and infrared studies on well-defined dispersed Pt clusters are combined here with first-principle theoretical methods on model cluster surfaces to probe the mechanism and structural requirements for CO oxidation catalysis at conditions typical of its industrial practice. CO oxidation turnover rates and the dynamics and thermodynamics of adsorption-desorption processes on cluster surfaces saturated with chemisorbed CO were measured on 1-20 nm Pt clusters under conditions of strict kinetic control. Turnover rates are proportional to O2 pressure and inversely proportional to CO pressure, consistent with kinetically relevant irreversible O2 activation steps on vacant sites present within saturated CO monolayers. These conclusions are consistent with the lack of isotopic scrambling in C16O-18O2-16O 2 reactions, and with infrared bands for chemisorbed CO that did not change within a CO pressure range that strongly influenced CO oxidation turnover rates. Density functional theory estimates of rate and equilibrium constants show that the kinetically relevant O2 activation steps involve direct O2* (or O2) reactions with CO* to form reactive O*-O-C*=O intermediates that decompose to form CO 2 and chemisorbed O*, instead of unassisted activation steps involving molecular adsorption and subsequent dissociation of O2. These CO-assisted O2 dissociation pathways avoid the higher barriers imposed by the spin-forbidden transitions required for unassisted O2 dissociation on surfaces saturated with chemisorbed CO. Measured rate parameters for CO oxidation were independent of Pt cluster size; these parameters depend on the ratio of rate constants for O2 reactions with CO* and CO adsorption equilibrium constants, which reflect the respective activation barriers and reaction enthalpies for these two steps. Infrared spectra during isotopic displacement and thermal desorption with 12CO- 13CO mixtures showed that the binding, dynamics, and thermodynamics of CO chemisorbed at saturation coverages do not depend on Pt cluster size in a range that strongly affects the coordination of Pt atoms exposed at cluster surfaces. These data and their theoretical and mechanistic interpretations indicate that the remarkable structure insensitivity observed for CO oxidation reactions reflects average CO binding properties that are essentially independent of cluster size. Theoretical estimates of rate and equilibrium constants for surface reactions and CO adsorption show that both parameters increase as the coordination of exposed Pt atoms decreases in Pt201 cluster surfaces; such compensation dampens but does not eliminate coordination and cluster size effects on measured rate constants. The structural features and intrinsic non-uniformity of cluster surfaces weaken when CO forms saturated monolayers on such surfaces, apparently because surfaces and adsorbates restructure to balance CO surface binding and CO-CO interaction energies. © 2011 American Chemical Society.
    Publisher
    American Chemical Society (ACS)
    Journal
    Journal of the American Chemical Society
    DOI
    10.1021/ja110073u
    PubMed ID
    21366255
    ae974a485f413a2113503eed53cd6c53
    10.1021/ja110073u
    Scopus Count
    Collections
    Articles; Biological and Environmental Sciences and Engineering (BESE) Division; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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