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dc.contributor.authorZhao, Zhun
Arentz, Joni
Pretzer, Lori A.
Limpornpipat, Pongsak
Clomburg, James M.
Gonzalez, Ramon
Schweitzer, Neil M.
Wu, Tianpin
Miller, Jeffrey T.
Wong, Michael S.
dc.date.accessioned 2014-08-08T17:24:34Z
dc.date.available 2014-08-08T17:24:34Z
dc.date.issued 2014
dc.identifier.citation Zhao, Zhun, Arentz, Joni, Pretzer, Lori A., et al.. "Volcano-shape glycerol oxidation activity of palladium-decorated gold nanoparticles." Chemical Science, (2014) Royal Society of Chemistry: http://dx.doi.org/10.1039/c4sc01001a.
dc.identifier.urihttps://hdl.handle.net/1911/76496
dc.description.abstract Bimetallic PdAu catalysts are more active than monometallic ones for the selective oxidation of alcohols, but the reasons for improvement remain insufficiently detailed. A metal-on-metal material can probe the structure–catalysis relationship more clearly than conventionally prepared bimetallics. In this study, Pd-on-Au nanoparticles with variable Pd surface coverages (sc%) ranging from 10 to 300 sc% were synthesized and immobilized onto carbon (Pd-on-Au/C). Tested for glycerol oxidation at 60 °C, pH 13.5, and 1 atm under flowing oxygen, the series of Pd-on-Au/C materials showed volcano-shape catalytic activity dependence on Pd surface coverage. Increasing surface coverage led to higher catalytic activity, such that initial turnover frequency (TOF) reached a maximum of ̴6000 h−1 at 80 sc%. Activity decreased above 80 sc% mostly due to catalyst deactivation. Pd-on-Au/C at 80 sc% was >10 times more active than monometallic Au/C and Pd/C, with both exhibiting TOF values less than [similar]500 h−1. Glyceric acid was the dominant primary reaction product for all compositions, with its zero-conversion selectivity varying monotonically as a function of Pd surface coverage. Glyceric acid yield from Pd-on-Au/C (80 sc%) was 42%, almost double the yields from Au/C and Pd/C (16% and 22%, respectively). Ex situ X-ray absorption near edge structure analysis of two Pd-on-Au/C materials with comparable activities (60 sc% and 150 sc%) showed that the former had less oxidized Pd ensembles than the latter, and that both catalysts were less oxidized compared to Pd/C. That Au stabilizes the metallic state of surface Pd atoms may be responsible for activity enhancement observed in other PdAu-catalyzed oxidation reactions. Decorating a Au surface with Pd generates a catalyst that has the deactivation resistance of Au, the higher glyceric acid selectivity of Pd, and the synergistically higher activities that neither metal has.
dc.language.iso eng
dc.publisher Royal Society of Chemistry
dc.rights This Open Access Article is licensed under a Creative Commons Attribution-Non Commercial 3.0 Unported Licence
dc.rights.urihttps://creativecommons.org/licenses/by-nc/3.0/
dc.title Volcano-shape glycerol oxidation activity of palladium-decorated gold nanoparticles
dc.type Journal article
dc.contributor.funder National Science Foundation
dc.contributor.funder Welch Foundation
dc.contributor.funder Sigma Xi Grants-in-Aid of Research
dc.contributor.funder U. S. Department of Energy, Office of Science, and Office of Basic Energy Sciences
dc.citation.journalTitle Chemical Science
dc.type.dcmi Text
dc.identifier.doihttp://dx.doi.org/10.1039/c4sc01001a
dc.identifier.grantID CBET-1134535 (National Science Foundation)
dc.identifier.grantID C-1676 (Welch Foundation)
dc.identifier.grantID G20111015157503 (Sigma Xi Grants-in-Aid of Research)
dc.identifier.grantID EEC-0813570 (National Science Foundation)
dc.identifier.grantID DE-AC02-06CH11357 (U. S. Department of Energy, Office of Science, and Office of Basic Energy Sciences)
dc.type.publication publisher version


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This Open Access Article is licensed under a Creative Commons Attribution-Non Commercial 3.0 Unported Licence
Except where otherwise noted, this item's license is described as This Open Access Article is licensed under a Creative Commons Attribution-Non Commercial 3.0 Unported Licence