skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit

Abstract

Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One definite approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum–copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C–C bond scission that leads to loss of selectivity and catalyst deactivation. γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions.

Authors:
 [1];  [1];  [1];  [1];  [2];  [1];  [1]
  1. Tufts Univ., Medford, MA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1223384
Grant/Contract Number:  
AC02-06CH11357; FG02-05ER15730; AC05-00OR22725; SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical sciences; catalysis; material science; physical chemistry

Citation Formats

Lucci, Felicia R., Liu, Jilei, Marcinkowski, Matthew D., Yang, Ming, Allard, Lawrence F., Flytzani-Stephanopoulos, Maria, and Sykes, E. Charles H. Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit. United States: N. p., 2015. Web. doi:10.1038/ncomms9550.
Lucci, Felicia R., Liu, Jilei, Marcinkowski, Matthew D., Yang, Ming, Allard, Lawrence F., Flytzani-Stephanopoulos, Maria, & Sykes, E. Charles H. Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit. United States. doi:10.1038/ncomms9550.
Lucci, Felicia R., Liu, Jilei, Marcinkowski, Matthew D., Yang, Ming, Allard, Lawrence F., Flytzani-Stephanopoulos, Maria, and Sykes, E. Charles H. Fri . "Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit". United States. doi:10.1038/ncomms9550. https://www.osti.gov/servlets/purl/1223384.
@article{osti_1223384,
title = {Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit},
author = {Lucci, Felicia R. and Liu, Jilei and Marcinkowski, Matthew D. and Yang, Ming and Allard, Lawrence F. and Flytzani-Stephanopoulos, Maria and Sykes, E. Charles H.},
abstractNote = {Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One definite approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum–copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C–C bond scission that leads to loss of selectivity and catalyst deactivation. γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions.},
doi = {10.1038/ncomms9550},
journal = {Nature Communications},
number = ,
volume = 6,
place = {United States},
year = {2015},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 57 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces
journal, February 2007

  • Stamenkovic, Vojislav R.; Mun, Bongjin Simon; Arenz, Matthias
  • Nature Materials, Vol. 6, Issue 3, p. 241-247
  • DOI: 10.1038/nmat1840

Isomerization and hydrocracking of C9 through C16 n-alkanes on Pt/HZSM-5 zeolite
journal, October 1983


A review of PEM hydrogen fuel cell contamination: Impacts, mechanisms, and mitigation
journal, March 2007


State of the art of multi-fuel reformers for fuel cell vehicles: problem identification and research needs
journal, March 2001


Alkali-Stabilized Pt-OHx Species Catalyze Low-Temperature Water-Gas Shift Reactions
journal, September 2010


Catalytically active Au-O(OH) x - species stabilized by alkali ions on zeolites and mesoporous oxides
journal, November 2014


Single-atom catalysis of CO oxidation using Pt1/FeOx
journal, July 2011

  • Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng
  • Nature Chemistry, Vol. 3, Issue 8
  • DOI: 10.1038/nchem.1095

Steam reforming of methanol over ceria and gold-ceria nanoshapes
journal, March 2010


‘Shape effects’ in metal oxide supported nanoscale gold catalysts
journal, January 2011

  • Boucher, Matthew B.; Goergen, Simone; Yi, Nan
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 7
  • DOI: 10.1039/c0cp02009e

Design of a Surface Alloy Catalyst for Steam Reforming
journal, March 1998


Isolated Metal Atom Geometries as a Strategy for Selective Heterogeneous Hydrogenations
journal, March 2012

  • Kyriakou, Georgios; Boucher, Matthew B.; Jewell, April D.
  • Science, Vol. 335, Issue 6073
  • DOI: 10.1126/science.1215864

Single atom alloy surface analogs in Pd0.18Cu15 nanoparticles for selective hydrogenation reactions
journal, January 2013

  • Boucher, Matthew B.; Zugic, Branko; Cladaras, George
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 29
  • DOI: 10.1039/c3cp51538a

Cu/Al 2 O 3 catalysts modified with Pd for selective acetylene hydrogenation
journal, November 2014


Surface free energies of solid metals: Estimation from liquid surface tension measurements
journal, January 1977


Hydrogen adsorption on and spillover from Au- and Cu-supported Pt3 and Pd3 clusters: a density functional study
journal, January 2012

  • Santana, Juan A.; Rösch, Notker
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 46
  • DOI: 10.1039/c2cp43080k

Atomic-Scale Imaging and Electronic Structure Determination of Catalytic Sites on Pd/Cu Near Surface Alloys
journal, March 2009

  • Tierney, Heather L.; Baber, Ashleigh E.; Sykes, E. Charles H.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 17
  • DOI: 10.1021/jp809766d

Atomic Scale Surface Structure of Pt/Cu(111) Surface Alloys
journal, January 2014

  • Lucci, Felicia R.; Lawton, Timothy J.; Pronschinske, Alex
  • The Journal of Physical Chemistry C, Vol. 118, Issue 6
  • DOI: 10.1021/jp405254z

Review of Pt-Based Bimetallic Catalysis: From Model Surfaces to Supported Catalysts
journal, August 2012

  • Yu, Weiting; Porosoff, Marc D.; Chen, Jingguang G.
  • Chemical Reviews, Vol. 112, Issue 11, p. 5780-5817
  • DOI: 10.1021/cr300096b

Isolated Pd Sites on the Intermetallic PdGa(111) and PdGa($\bar 1$$\bar 1$$\bar 1$) Model Catalyst Surfaces
journal, August 2012

  • Prinz, Jan; Gaspari, Roberto; Pignedoli, Carlo A.
  • Angewandte Chemie, Vol. 124, Issue 37
  • DOI: 10.1002/ange.201203787

Low-temperature 1,3-butadiene hydrogenation over supported Pt/3d/γ-Al2O3 bimetallic catalysts☆
journal, February 2011


Alloy catalysts designed from first principles
journal, October 2004

  • Greeley, Jeff; Mavrikakis, Manos
  • Nature Materials, Vol. 3, Issue 11
  • DOI: 10.1038/nmat1223

Adsorption of Unsaturated Hydrocarbons on Pd(111) and Pt(111): A DFT Study
journal, November 2003

  • Mittendorfer, Florian; Thomazeau, C.; Raybaud, P.
  • The Journal of Physical Chemistry B, Vol. 107, Issue 44
  • DOI: 10.1021/jp035660f

Selectivity Control for the Catalytic 1,3-Butadiene Hydrogenation on Pt(111) and Pd(111) Surfaces:  Radical versus Closed-Shell Intermediates
journal, July 2005

  • Valcárcel, Ana; Clotet, Anna; Ricart, Josep M.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 29
  • DOI: 10.1021/jp052087m

The adsorption of CO, O2, and H2 on Pt
journal, December 1977


Adsorption and desorption kinetics in the systems H2/Cu(111), H2/Cu(110) and H2/Cu(100)
journal, October 1989


Interaction of hydrogen with Cu3Pt(111): dissociation via isolated platinum atoms
journal, April 1994


Catalytic Activity of Single Transition-Metal Atom Doped in Cu(111) Surface for Heterogeneous Hydrogenation
journal, July 2013

  • Fu, Qiang; Luo, Yi
  • The Journal of Physical Chemistry C, Vol. 117, Issue 28
  • DOI: 10.1021/jp403902g

Quantum Tunneling Enabled Self-Assembly of Hydrogen Atoms on Cu(111)
journal, October 2012

  • Jewell, April D.; Peng, Guowen; Mattera, Michael F. G.
  • ACS Nano, Vol. 6, Issue 11
  • DOI: 10.1021/nn3038463

Large-scale, density functional theory-based screening of alloys for hydrogen evolution
journal, March 2007


Dissociative adsorption dynamics of H2 at the atop-Pt, atop-Cu, and CuPt bridge sites of an ordered Cu3Pt(111) — orientational effects
journal, January 2001


New developments in hydrogenation catalysis particularly in synthesis of fine and intermediate chemicals
journal, February 2005


Hydrogenation of ethylene over platinum (111) single-crystal surfaces
journal, April 1984

  • Zaera, F.; Somorjai, G. A.
  • Journal of the American Chemical Society, Vol. 106, Issue 8
  • DOI: 10.1021/ja00320a013

An Investigation of the Reaction Pathway for Ethylene Hydrogenation on Pd(111)
journal, November 2001

  • Stacchiola, D.; Azad, S.; Burkholder, L.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 45
  • DOI: 10.1021/jp012553h

Selective Hydrogenation and H-D Exchange of Unsaturated Hydrocarbons on Pd(100)-P(1×1)-H(D)
journal, September 1995


Isomerization and Hydrogenation of cis -2-Butene on Pd Model Catalyst
journal, July 2008

  • Brandt, Björn; Fischer, Jan-Henrik; Ludwig, Wiebke
  • The Journal of Physical Chemistry C, Vol. 112, Issue 30
  • DOI: 10.1021/jp800205j

Site-blocking effects of preadsorbed H on Pt(111) probed by 1,3-butadiene adsorption and reaction
journal, December 2009


Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy
journal, January 2013

  • Michalak, William D.; Krier, James M.; Komvopoulos, Kyriakos
  • The Journal of Physical Chemistry C, Vol. 117, Issue 4
  • DOI: 10.1021/jp311772p

Hydrogenation of 1,3-butadiene on two ordered Sn/Pt(111) surface alloys
journal, August 2005


Controlling a spillover pathway with the molecular cork effect
journal, April 2013

  • Marcinkowski, Matthew D.; Jewell, April D.; Stamatakis, Michail
  • Nature Materials, Vol. 12, Issue 6
  • DOI: 10.1038/nmat3620

Adsorption properties and formation of surface alloys
journal, May 1996


Bimetallic nanoparticles of PtM (M=Au, Cu, Ni) supported on iron oxide: Radiolytic synthesis and CO oxidation catalysis
journal, October 2010


Atomically Dispersed Au–(OH) x Species Bound on Titania Catalyze the Low-Temperature Water-Gas Shift Reaction
journal, March 2013

  • Yang, Ming; Allard, Lawrence F.; Flytzani-Stephanopoulos, Maria
  • Journal of the American Chemical Society, Vol. 135, Issue 10
  • DOI: 10.1021/ja312646d

Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina
journal, September 2014

  • Peterson, Eric J.; DeLaRiva, Andrew T.; Lin, Sen
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5885

Bimetallic Au–Pd catalysts for selective hydrogenation of butadiene: Influence of the preparation method on catalytic properties
journal, January 2013


Adsorption and reaction of 1,3-butadiene on Pt(111) and Sn/Pt(111) surface alloys
journal, November 2004


    Works referencing / citing this record:

    The Role of Supported Atomically Distributed Metal Species in Electrochemistry and How to Create Them
    journal, May 2019

    • Ding, Yuxiao; Schlögl, Robert; Heumann, Saskia
    • ChemElectroChem, Vol. 6, Issue 15
    • DOI: 10.1002/celc.201900598