Understanding the Intrinsic Surface Reactivity of Single-Layer and Multilayer PdO(101) on Pd(100)

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Understanding the Intrinsic Surface Reactivity of Single-Layer and Multilayer PdO(101) on Pd(100)

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dc.contributor.author Mehar, Vikram
dc.contributor.author Kim, Minkyu
dc.contributor.author Shipilin, Mikhail
dc.contributor.author Van den Bossche, Maxime
dc.contributor.author Gustafson, Johan
dc.contributor.author Merte, Lindsay Richard
dc.contributor.author Hejral, Uta
dc.contributor.author Gronbeck, Henrik
dc.contributor.author Lundgren, Edvin
dc.contributor.author Asthagiri, Aravind
dc.contributor.author Weaver, Jason F.
dc.date.accessioned 2018-11-01T16:12:17Z
dc.date.available 2018-11-01T16:12:17Z
dc.date.issued 2018 en_US
dc.identifier.issn 2155-5435 en_US
dc.identifier.uri http://hdl.handle.net/2043/26698
dc.description.abstract We investigated the intrinsic reactivity of CO on single-layer and multilayer PdO(101) grown on Pd(100) using temperature-programmed reaction spectroscopy (TPRS) and reflection absorption infrared spectroscopy (RAIRS) experiments, as well as density functional theory (DFT) calculations. We find that CO binds more strongly on multilayer than single-layer PdO(101) (similar to 119 kJ/mol vs 43 kJ/mol), and that CO oxidizes negligibly on single-layer PdO(101), whereas nearly 90% of a saturated layer of CO oxidizes on multilayer PdO(101) during TPRS experiments. RAIRS further shows that CO molecules adsorb on both bridge-Pd-cus and atop-Pd-cus sites (coordinatively unsaturated Pd sites) of single-layer PdO(101)/Pd(100), while CO binds exclusively on atop-Pd-cus sites of multilayer PdO(101). The DFT calculations reproduce the much stronger binding of CO on multilayer PdO(101), as well as the observed binding site preferences, and reveal that the stronger binding is entirely responsible for the higher CO oxidation activity of multilayer PdO(101)/Pd(100). We show that the O atom below the Pd-cus site, present only on multilayer PdO(101), modifies the electronic states of the Pd-cus, atom in a way that enhances the CO-Pd-cus bonding. Lastly, we show that a precursor -mediated kinetic model, with energetics determined from the present study, predicts that the intrinsic CO oxidation rates achieved on both single-layer and multilayer PdO(101)/Pd(100) can be expected to exceed the gaseous CO diffusion rate to the surface during steady-state CO oxidation at elevated pressures, even though the intrinsic reaction rates are 4-5 orders of magnitude lower on single-layer PdO(101)/Pd(100) than on multilayer PdO(101)/Pd(100). en_US
dc.format.extent 15
dc.language.iso eng en_US
dc.publisher American Chemical Society en_US
dc.subject CO oxidation en_US
dc.subject Pd(100) en_US
dc.subject PdO en_US
dc.subject palladium en_US
dc.subject infrared spectroscopy en_US
dc.subject RAIRS en_US
dc.subject DFT en_US
dc.subject surface oxide en_US
dc.subject.classification Sciences en_US
dc.title Understanding the Intrinsic Surface Reactivity of Single-Layer and Multilayer PdO(101) on Pd(100) en_US
dc.type Article, peer reviewed scientific en_US
dc.contributor.department Malmö University. Faculty of Technology and Society
dc.identifier.doi 10.1021/acscatal.8b02191 en_US
dc.subject.srsc Research Subject Categories::NATURAL SCIENCES en_US
dc.relation.ispartofpublication ACS Catalysis;9
dc.relation.ispartofpublicationvolume 8 en_US
dc.description.authorversion No en_US
dc.format.ePage 8567
dc.format.sPage 8553
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