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Isolated Metal Atom Geometries As A Strategy For Selective Heterogeneous Hydrogenations

G. Kyriakou, M. B. Boucher, A. D. Jewell, E. Lewis, T. J. Lawton, A. Baber, Heather L. R. Tierney, M. Flytzani-Stephanopoulos, E. Sykes
Published 2012 · Chemistry, Medicine

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Tuning Hydrogen Adsorption Heterogeneous metal catalysts for hydrogenating unsaturated organic compounds need to bind molecular hydrogen strongly enough that it dissociates and forms adsorbed hydrogen atoms, but must not bind these atoms too strongly, or the transfer to the organic molecule will be impeded. Kyriakou et al. (p. 1209) examined surface alloy catalysts created when palladium (Pd) atoms are adsorbed on a copper (Cu) surface using scanning tunneling microscopy and desorption techniques under ultrahigh vacuum conditions. The Pd atoms could bind hydrogen dissociatively—which, under these conditions, the Cu surfaces could not—allowing the Cu surface to take up adsorbed hydrogen atoms. These weakly bound hydrogen atoms were able to selectively hydrogenate styrene and acetylene. Palladium atoms adsorbed on a copper surface activate hydrogen adsorption for subsequent hydrogenation reactions. Facile dissociation of reactants and weak binding of intermediates are key requirements for efficient and selective catalysis. However, these two variables are intimately linked in a way that does not generally allow the optimization of both properties simultaneously. By using desorption measurements in combination with high-resolution scanning tunneling microscopy, we show that individual, isolated Pd atoms in a Cu surface substantially lower the energy barrier to both hydrogen uptake on and subsequent desorption from the Cu metal surface. This facile hydrogen dissociation at Pd atom sites and weak binding to Cu allow for very selective hydrogenation of styrene and acetylene as compared with pure Cu or Pd metal alone.
This paper references
10.1016/0167-2584(89)90691-9
Adsorption and desorption kinetics in the systems H2/Cu(111), H2/Cu(110) and H2/Cu(100)
G. Anger (1989)
10.1021/JA0700855
A Cu/Pt near-surface alloy for water-gas shift catalysis.
J. Knudsen (2007)
10.1021/JP800205J
Isomerization and Hydrogenation of cis-2-Butene on Pd Model Catalyst
B. Brandt (2008)
10.1021/JP903541K
Importance of Kinetics in Surface Alloying: A Comparison of the Diffusion Pathways of Pd and Ag Atoms on Cu(111)
Darin O. Bellisario (2009)
10.1016/J.SUSC.2007.10.042
Hydrogen adsorption on Ru(001) studied by Scanning Tunneling Microscopy
M. Tatarkhanov (2008)
10.1038/nature01557
Dissociative hydrogen adsorption on palladium requires aggregates of three or more vacancies
T. Mitsui (2003)
10.1016/S0039-6028(03)00822-7
Hydrogen adsorption and diffusion on Pd(1 1 1)
T. Mitsui (2003)
10.1016/J.SUSC.2004.09.016
Adsorption of styrene on Ag(111)
W. Wei (2004)
10.1063/1.480145
Interaction of H atoms with Cu(111) surfaces: Adsorption, absorption, and abstraction
T. Kammler (1999)
10.1016/S0039-6028(98)00124-1
Submonolayer growth of Pd on Cu(111) studied by scanning tunneling microscopy
A. B. Aaen (1998)
10.1126/science.1183591
Nanoporous Gold Catalysts for Selective Gas-Phase Oxidative Coupling of Methanol at Low Temperature
A. Wittstock (2010)
10.1021/JA00233A038
Epoxidation of olefins on silver: conversion of norbornene to norbornene oxide by atomic oxygen on silver(110)
J. Roberts (1988)
Chem
H.-L. Jiang
10.1039/B509629D
A highly active catalyst for CO oxidation at 298 K: mononuclear AuIII complexes anchored to La2O3 nanoparticles.
J. C. Fierro-González (2005)
10.1039/C1JM12020D
Recent progress in synergistic catalysis over heterometallic nanoparticles
H. Jiang (2011)
10.1016/J.SUSC.2004.02.040
Hydrogen adsorption energies on bimetallic overlayer systems at the solid-vacuum and the solid-liquid interface
A. Roudgar (2005)
10.1063/1.2991434
Structure and reactions of carbon and hydrogen on Ru(0001): a scanning tunneling microscopy study.
T. Shimizu (2008)
10.1021/JP003349H
Theoretical Study of the Interaction of Molecular Hydrogen with PdCu(111) Bimetallic Surfaces
C. Sousa (2001)
10.1016/0167-2584(87)90365-3
Effect of surface temperature on the sorption of hydrogen by Pd(111)
G. Gdowski (1987)
10.1126/science.1164170
Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles
F. Tao (2008)
10.1016/0039-6028(87)90187-7
Surface science lettersEffect of surface temperature on the sorption of hydrogen by Pd(111)
G. Gdowski (1987)
10.1021/JA9922476
Acetylene cyclotrimerization on supported size-selected Pd-n clusters (1 <= n <= 30): one atom is enough!
S. Abbet (2000)
10.1038/nmat3123
Turning aluminium into a noble-metal-like catalyst for low-temperature activation of molecular hydrogen.
I. Chopra (2011)
10.1021/JP809766D
Atomic-scale imaging and electronic structure determination of catalytic sites on Pd/Cu near surface alloys
Heather L. R. Tierney (2009)
Methods and additional data are available as supporting material on Science Online
10.1103/PHYSREVLETT.103.246102
Hydrogen dissociation and spillover on individual isolated palladium atoms.
Heather L. R. Tierney (2009)
10.1007/S11244-011-9677-Y
Can a Single Atom Serve as the Active Site in Some Heterogeneous Catalysts?
J. Thomas (2011)
10.1021/JP044213C
Acetylene coupling on Cu(111): formation of butadiene, benzene, and cyclooctatetraene.
G. Kyriakou (2005)
10.1039/C39830000623
Low temperature catalytic chemistry of the Pd(111) surface: benzene and ethylene from acetylene
W. Tysoe (1983)
10.1021/JP0548927
Reforming of oxygenates for H2 production: correlating reactivity of ethylene glycol and ethanol on Pt(111) and Ni/Pt(111) with surface d-band center.
Orest Skoplyak (2006)
10.1126/science.1192449
Alkali-Stabilized Pt-OHx Species Catalyze Low-Temperature Water-Gas Shift Reactions
Y. Zhai (2010)
Chem
G. Kyriakou
10.1021/JP046540Q
Surface and subsurface hydrogen: adsorption properties on transition metals and near-surface alloys.
J. Greeley (2005)
10.1006/JCAT.1996.0404
Surface and bulk characterisation of metallic phases present during CO hydrogenation over Pd-Cu/KL zeolite catalysts
J. A. Anderson (1996)
10.1103/PHYSREVLETT.85.4566
Direct observation of the quantum tunneling of single hydrogen atoms with a scanning tunneling microscope
Lauhon (2000)
10.1038/NMAT1223
Alloy catalysts designed from first principles
J. Greeley (2004)
10.1126/SCIENCE.279.5358.1913
Design of a surface alloy catalyst for steam reforming
Besenbacher (1998)
10.1016/0039-6028(74)90060-0
Adsorption of hydrogen on palladium single crystal surfaces
H. Conrad (1974)
10.1038/nmat2156
Ru-Pt core-shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen.
Selim Alayoǧlu (2008)
10.1021/JP201793D
High-throughput Characterization of Surface Segregation in CuxPd1-x Alloys
D. Priyadarshini (2011)



This paper is referenced by
10.1007/s10562-013-1064-9
Noble Metal Promoted CeO2–ZrO2-Supported Ni Catalysts for Liquid-Phase Hydrogenation of Cinnamaldehyde
S. Bhogeswararao (2013)
10.1021/am301814y
Synthesis of octopus-tentacle-like Cu nanowire-Ag nanocrystals heterostructures and their enhanced electrocatalytic performance for oxygen reduction reaction.
M. Han (2012)
ect of single pd atoms on the energetics of recombinative O 2 desorption from Au ( 111 )
Felicia R. Luccia (2018)
The Reactivity of Multifunctional Alcohols on Palladium Surfaces and Supported Catalysts
Michael B. Griffin (2013)
10.1002/CNMA.201800022
Selective Semihydrogenation of Phenylacetylene to Styrene Catalyzed by Alloyed Palladium/Gold Catalysts Anchored on Cerium Oxide
S. Zhang (2018)
10.1002/CELC.201800507
Single‐Atom Catalysts for the Hydrogen Evolution Reaction
Haoxuan Liu (2018)
10.1039/C5RA07433A
New insights into structure–activity relationships for propane hydrogenolysis over Ni–Cu bimetallic catalysts
Y. Yao (2015)
10.1039/C6TA04315A
Ultrasmall nanoparticles and pseudo-single atoms of platinum supported on fibrous nanosilica (KCC-1/Pt): engineering selectivity of hydrogenation reactions
Mahak Dhiman (2016)
10.1038/ncomms9668
Atomic cobalt on nitrogen-doped graphene for hydrogen generation
H. Fei (2015)
10.1016/J.JELECHEM.2019.113279
Recent progress of Pt-based catalysts for oxygen reduction reaction in preparation strategies and catalytic mechanism
Shijie Yi (2019)
10.1007/s12274-019-2351-6
Insight of the stability and activity of platinum single atoms on ceria
Xuxu Ye (2019)
10.1002/ANGE.201904614
General π‐electron‐assisted strategy for constructing transition metal single‐atom electrocatalysts with bi‐functional active sites toward highly efficient water splitting
Weihong Lai (2019)
10.1088/1361-6528/ab81c4
Pt nanoparticles anchored on rare metal oxide coated on SBA-15: a highly active catalyst for synergistic catalytichydrogenation of benzaldehyde.
Y. Zhang (2020)
10.1002/advs.202001069
Metal‐Nitrogen‐Doped Carbon Materials as Highly Efficient Catalysts: Progress and Rational Design
Zhangsheng Shi (2020)
10.1007/s10562-019-02709-7
Single-Atom Catalysis: How Structure Influences Catalytic Performance
G. S. Parkinson (2019)
10.1016/B978-0-08-097774-4.00713-0
Hydrogenation Reactions: Concepts and Practice
L. Guczi (2013)
10.1021/nl503519m
Configurational thermodynamics of alloyed nanoparticles with adsorbates.
L. Wang (2014)
10.1016/J.MATCHEMPHYS.2017.01.047
Combining Ru, Ni and Ni(OH)2 active sites for improving catalytic performance in benzene hydrogenation
L. Zhu (2017)
10.1007/s12274-016-1256-x
New mechanistic pathways for CO oxidation catalyzed by single-atom catalysts: Supported and doped Au1/ThO2
B. Long (2016)
10.1039/c8nr05179h
Single atom alloy catalyst for SO3 decomposition: enhancement of platinum catalyst's performance by Ag atom embedding.
S. Nigam (2018)
10.1021/ACSCATAL.5B01522
Oxygen-Deficient Tungsten Oxide as Versatile and Efficient Hydrogenation Catalyst
J. Song (2015)
Elucidating the Effect of the Lateral Interactions on the Adsorption of Bio-Oil Model Compounds on Pt ( 111 )
F. Abild-Pedersen (2018)
10.1021/ACSCATAL.6B00530
Activity and Selectivity in Nitroarene Hydrogenation over Au Nanoparticles on the Edge/Corner of Anatase
L. Wang (2016)
10.1021/ACSCATAL.5B01586
Nanoporous Gold: Understanding the Origin of the Reactivity of a 21st Century Catalyst Made by Pre-Columbian Technology
J. Biener (2015)
10.1021/JP508625B
Dehydrogenation of Propane to Propylene by a Pd/Cu Single-Atom Catalyst: Insight from First-Principles Calculations
Xinrui Cao (2015)
10.1021/ACS.JPCC.6B03461
Computational Investigation of Fe–Cu Bimetallic Catalysts for CO2 Hydrogenation
X. Nie (2016)
10.1016/s1872-2067(19)63392-9
Some insight on the structure/activity relationship of metal nanoparticles in Cu/SiO2 catalysts
N. Scotti (2019)
10.1039/d0ta00334d
Probing composition distributions in nanoalloy catalysts with correlative electron microscopy
Shikai Liu (2020)
10.1021/JP4070328
Tungsten Carbide Supports for Single-Atom Platinum-Based Fuel-Cell Catalysts: First-Principles Study on the Metal–Support Interactions and O2 Dissociation on WxC Low-Index Surfaces
C. K. Poh (2014)
10.1007/s40843-020-1426-0
Selective hydrogenation of acetylene on graphene-supported non-noble metal single-atom catalysts
Hongying Zhuo (2020)
10.1039/D0SC03523H
Ion-molecule reactions catalyzed by a single gold atom
S. Yang (2020)
10.1016/j.cattod.2020.03.052
Restructuring effects of the chemical environment in metal nanocatalysis and single-atom catalysis
L. Piccolo (2020)
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