title: Synergistic Effects in Bimetallic Palladium-Copper Catalysts Improve Selectivity in Oxygenate Coupling Reactions.
abstract: Condensation reactions such as Guerbet and aldol are important since they allow for C-C bond formation and give higher molecular weight oxygenates. An initial study identified Pd-supported on hydrotalcite as an active catalyst for the transformation, although this catalyst showed extensive undesirable decarbonylation. A catalyst containing Pd and Cu in a 3:1 ratio dramatically decreased decarbonylation, while preserving the high catalytic rates seen with Pd-based catalysts. A combination of XRD, EXAFS, TEM, and CO chemisorption and TPD revealed the formation of CuPd bimetallic nanoparticles with a Cu-enriched surface. Finally, density functional theory studies suggest that the surface segregation of Cu atoms in the bimetallic alloy catalyst produces Cu sites with increased reactivity, while the Pd sites responsible for unselective decarbonylation pathways are selectively poisoned by CO.
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.|Department of Chemical and Biomolecular Engineering, University of California , Berkeley, California 94720, United States.|Energy Biosciences Institute, University of California , Berkeley, California 94720, United States.
authors.forename: Konstantinos A
authors.initials: KA
authors.lastname: Goulas
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.|Energy Biosciences Institute, University of California , Berkeley, California 94720, United States.
authors.forename: Sanil
authors.initials: S
authors.lastname: Sreekumar
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of Houston , Houston, Texas 77204, United States.
authors.forename: Yuying
authors.initials: Y
authors.lastname: Song
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of Houston , Houston, Texas 77204, United States.
authors.forename: Purnima
authors.initials: P
authors.lastname: Kharidehal
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.|Energy Biosciences Institute, University of California , Berkeley, California 94720, United States.
authors.forename: Gorkem
authors.initials: G
authors.lastname: Gunbas
authors.affiliation: BP North America , Naperville, Illinois 60563, United States.
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Dietrich
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California , Berkeley, California 94720, United States.
authors.forename: Gregory R
authors.initials: GR
authors.lastname: Johnson
authors.affiliation: BP North America , Naperville, Illinois 60563, United States.
authors.forename: Y C
authors.initials: YC
authors.lastname: Wang
authors.affiliation: Energy Biosciences Institute, University of California , Berkeley, California 94720, United States.
authors.forename: Adam M
authors.initials: AM
authors.lastname: Grippo
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of Houston , Houston, Texas 77204, United States.
authors.forename: Lars C
authors.initials: LC
authors.lastname: Grabow
authors.affiliation: Energy Biosciences Institute, University of California , Berkeley, California 94720, United States.|BP North America , Naperville, Illinois 60563, United States.
authors.forename: Amit A
authors.initials: AA
authors.lastname: Gokhale
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.|Energy Biosciences Institute, University of California , Berkeley, California 94720, United States.
authors.forename: F Dean
authors.initials: FD
authors.lastname: Toste