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

Title: Designing Efficient Catalysts through Bimetallic Architecture: Rh@Pt Nanocubes as a Case Study

Abstract

Bimetallic nanocatalysts often have increased activities and stabilities over their monometallic counterparts due to surface strain effects and electron transfer between the two metals. We demonstrate that the performance of a nanocatalyst can be precisely manipulated in shape-controlled nanocrystals through a bimetallic core@shell architecture. This ability is achieved in a model core@shell Rh@Pt nanocube system through control of shell thickness. The enhanced performance with thin-shelled nanocrystals is correlated with the weakening of surface–adsorbate interactions. In these thin-shelled Rh@Pt nanocubes, the maximum current density achieved during formic acid oxidation was over 2 times greater than that achieved with similarly sized Pt nanocubes, with a decreased CO poisoning ratio as well. Finally, the strategy employed here should also enhance the performance of many other bimetallic nanomaterials composed of more cost-effective metals too.

Authors:
 [1];  [1];  [2];  [1]; ORCiD logo [1]
  1. Indiana Univ., Bloomington, IN (United States). Dept. of Chemistry
  2. Rockhurst Univ., Kansas City, MO (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Indiana Univ., Bloomington, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1482343
Alternate Identifier(s):
OSTI ID: 1377949
Grant/Contract Number:  
SC0010489; CHE-1048613; DMR-1126394
Resource Type:
Accepted Manuscript
Journal Name:
ChemNanoMat
Additional Journal Information:
Journal Volume: 3; Journal Issue: 11; Journal ID: ISSN 2199-692X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; bimetallic nanoparticles; formic acid oxidation; platinum; rhodium; Sabatier principle

Citation Formats

Harak, Ethan W., Koczkur, Kallum M., Harak, Dale W., Patton, Paul, and Skrabalak, Sara E. Designing Efficient Catalysts through Bimetallic Architecture: Rh@Pt Nanocubes as a Case Study. United States: N. p., 2017. Web. doi:10.1002/cnma.201700167.
Harak, Ethan W., Koczkur, Kallum M., Harak, Dale W., Patton, Paul, & Skrabalak, Sara E. Designing Efficient Catalysts through Bimetallic Architecture: Rh@Pt Nanocubes as a Case Study. United States. doi:10.1002/cnma.201700167.
Harak, Ethan W., Koczkur, Kallum M., Harak, Dale W., Patton, Paul, and Skrabalak, Sara E. Wed . "Designing Efficient Catalysts through Bimetallic Architecture: Rh@Pt Nanocubes as a Case Study". United States. doi:10.1002/cnma.201700167. https://www.osti.gov/servlets/purl/1482343.
@article{osti_1482343,
title = {Designing Efficient Catalysts through Bimetallic Architecture: Rh@Pt Nanocubes as a Case Study},
author = {Harak, Ethan W. and Koczkur, Kallum M. and Harak, Dale W. and Patton, Paul and Skrabalak, Sara E.},
abstractNote = {Bimetallic nanocatalysts often have increased activities and stabilities over their monometallic counterparts due to surface strain effects and electron transfer between the two metals. We demonstrate that the performance of a nanocatalyst can be precisely manipulated in shape-controlled nanocrystals through a bimetallic core@shell architecture. This ability is achieved in a model core@shell Rh@Pt nanocube system through control of shell thickness. The enhanced performance with thin-shelled nanocrystals is correlated with the weakening of surface–adsorbate interactions. In these thin-shelled Rh@Pt nanocubes, the maximum current density achieved during formic acid oxidation was over 2 times greater than that achieved with similarly sized Pt nanocubes, with a decreased CO poisoning ratio as well. Finally, the strategy employed here should also enhance the performance of many other bimetallic nanomaterials composed of more cost-effective metals too.},
doi = {10.1002/cnma.201700167},
journal = {ChemNanoMat},
number = 11,
volume = 3,
place = {United States},
year = {2017},
month = {8}
}

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

Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: TEM images of Rh@Pt nanocubes with Pt shell thicknesses of (A) 1.2 ML (B) 2.6 ML (C) 5.6 ML and (D) 7.4 ML. The scatter plot in (E) shows the linear relationship between the amount of Pt(acac)2 used and the resulting Pt shell thickness. Scale bars are 5more » nm.« less

Save / Share:

Works referenced in this record:

Formic Acid Oxidation on Shape-Controlled Pt Nanoparticles Studied by Pulsed Voltammetry
journal, July 2010

  • Grozovski, Vitali; Solla-Gullón, José; Climent, Víctor
  • The Journal of Physical Chemistry C, Vol. 114, Issue 32
  • DOI: 10.1021/jp104755b

Rh−Pt Bimetallic Catalysts: Synthesis, Characterization, and Catalysis of Core−Shell, Alloy, and Monometallic Nanoparticles
journal, December 2008

  • Alayoglu, Selim; Eichhorn, Bryan
  • Journal of the American Chemical Society, Vol. 130, Issue 51
  • DOI: 10.1021/ja8061425

Size Effects of PVP−Pd Nanoparticles on the Catalytic Suzuki Reactions in Aqueous Solution
journal, June 2002

  • Li, Yin; Boone, Edna; El-Sayed, Mostafa A.
  • Langmuir, Vol. 18, Issue 12
  • DOI: 10.1021/la011469q

Seed-Mediated Co-reduction: A Versatile Route to Architecturally Controlled Bimetallic Nanostructures
journal, February 2012

  • DeSantis, Christopher J.; Sue, Aaron C.; Bower, Matthew M.
  • ACS Nano, Vol. 6, Issue 3
  • DOI: 10.1021/nn2051168

Core-level shifts at the Pt/W(110) monolayer bimetallic interface
journal, December 2009


Shaping binary metal nanocrystals through epitaxial seeded growth
journal, July 2007

  • Habas, Susan E.; Lee, Hyunjoo; Radmilovic, Velimir
  • Nature Materials, Vol. 6, Issue 9
  • DOI: 10.1038/nmat1957

Role of Electronic Perturbation in Stability and Activity of Pt-Based Alloy Nanocatalysts for Oxygen Reduction
journal, November 2012

  • Hwang, Seung Jun; Kim, Soo-Kil; Lee, June-Gunn
  • Journal of the American Chemical Society, Vol. 134, Issue 48
  • DOI: 10.1021/ja307951y

Iodide-Mediated Control of Rhodium Epitaxial Growth on Well-Defined Noble Metal Nanocrystals: Synthesis, Characterization, and Structure-Dependent Catalytic Properties
journal, October 2012

  • Sneed, Brian T.; Kuo, Chun-Hong; Brodsky, Casey N.
  • Journal of the American Chemical Society, Vol. 134, Issue 44
  • DOI: 10.1021/ja308030h

Core-level shifts in bulk alloys and surface adlayers
journal, June 1995


Structural effects in electrocatalysis: oxygen reduction on platinum low index single-crystal surfaces in perchloric acid solutions
journal, October 1994

  • Marković, N. M.; Adžić, R. R.; Cahan, B. D.
  • Journal of Electroanalytical Chemistry, Vol. 377, Issue 1-2
  • DOI: 10.1016/0022-0728(94)03467-2

Explicit Detection of the Mechanism of Platinum Nanoparticle Shape Control by Polyvinylpyrrolidone
journal, March 2016

  • Ye, Jin-Yu; Attard, Gary A.; Brew, Ashley
  • The Journal of Physical Chemistry C, Vol. 120, Issue 14
  • DOI: 10.1021/acs.jpcc.5b10910

Facile Synthesis of Rhodium Icosahedra with Controlled Sizes up to 12 nm
journal, September 2015


The Ligand Effect: CO Desorption from Pt/Ru Catalysts
journal, December 2005


Ru–Pt core–shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen
journal, March 2008

  • Alayoglu, Selim; Nilekar, Anand U.; Mavrikakis, Manos
  • Nature Materials, Vol. 7, Issue 4, p. 333-338
  • DOI: 10.1038/nmat2156

Surface lattice-engineered bimetallic nanoparticles and their catalytic properties
journal, January 2012

  • Wu, Jianbo; Li, Panpan; Pan, Yung-Tin (Frank)
  • Chemical Society Reviews, Vol. 41, Issue 24
  • DOI: 10.1039/c2cs35189g

High-Indexed Pt 3 Fe Nanocatalysts and Their Enhanced Catalytic Performance in Dual Organic Reactions
journal, June 2015


Synthesis, Shape Control, and Methanol Electro-oxidation Properties of Pt–Zn Alloy and Pt 3 Zn Intermetallic Nanocrystals
journal, May 2012

  • Kang, Yijin; Pyo, Jun Beom; Ye, Xingchen
  • ACS Nano, Vol. 6, Issue 6
  • DOI: 10.1021/nn301583g

Building up strain in colloidal metal nanoparticle catalysts
journal, January 2015

  • Sneed, Brian T.; Young, Allison P.; Tsung, Chia-Kuang
  • Nanoscale, Vol. 7, Issue 29
  • DOI: 10.1039/C5NR02529J

Shape-Dependent Catalytic Activity of Platinum Nanoparticles in Colloidal Solution
journal, July 2004

  • Narayanan, Radha; El-Sayed, Mostafa A.
  • Nano Letters, Vol. 4, Issue 7
  • DOI: 10.1021/nl0495256

Enhancing the catalytic and electrocatalytic properties of Pt-based catalysts by forming bimetallic nanocrystals with Pd
journal, January 2012

  • Zhang, Hui; Jin, Mingshang; Xia, Younan
  • Chemical Society Reviews, Vol. 41, Issue 24
  • DOI: 10.1039/c2cs35173k

Effect of Pd Nanoparticle Size on the Catalytic Hydrogenation of Allyl Alcohol
journal, April 2006

  • Wilson, Orla M.; Knecht, Marc R.; Garcia-Martinez, Joaquin C.
  • Journal of the American Chemical Society, Vol. 128, Issue 14, p. 4510-4511
  • DOI: 10.1021/ja058217m

A balancing act: manipulating reactivity of shape-controlled metal nanocatalysts through bimetallic architecture
journal, January 2016

  • Laskar, M.; Skrabalak, S. E.
  • Journal of Materials Chemistry A, Vol. 4, Issue 18
  • DOI: 10.1039/C5TA09368F

High-Index Facets Bounded Platinum–Lead Concave Nanocubes with Enhanced Electrocatalytic Properties
journal, May 2017


Seedless Growth of Palladium Nanocrystals with Tunable Structures: From Tetrahedra to Nanosheets
journal, October 2015


Sub-10 nm Platinum Nanocrystals with Size and Shape Control: Catalytic Study for Ethylene and Pyrrole Hydrogenation
journal, April 2009

  • Tsung, Chia-Kuang; Kuhn, John N.; Huang, Wenyu
  • Journal of the American Chemical Society, Vol. 131, Issue 16
  • DOI: 10.1021/ja809936n

Preferential CO Oxidation in Hydrogen: Reactivity of Core−Shell Nanoparticles
journal, June 2010

  • Nilekar, Anand Udaykumar; Alayoglu, Selim; Eichhorn, Bryan
  • Journal of the American Chemical Society, Vol. 132, Issue 21, p. 7418-7428
  • DOI: 10.1021/ja101108w

Surface segregation energies in low-index open surfaces of bimetallic transition metal alloys
journal, January 2009

  • Nilekar, Anand Udaykumar; Ruban, Andrei V.; Mavrikakis, Manos
  • Surface Science, Vol. 603, Issue 1
  • DOI: 10.1016/j.susc.2008.10.029

Nanoscale-Phase-Separated Pd–Rh Boxes Synthesized via Metal Migration: An Archetype for Studying Lattice Strain and Composition Effects in Electrocatalysis
journal, September 2013

  • Sneed, Brian T.; Brodsky, Casey N.; Kuo, Chun-Hong
  • Journal of the American Chemical Society, Vol. 135, Issue 39
  • DOI: 10.1021/ja405387q

Spiny Rhombic Dodecahedral CuPt Nanoframes with Enhanced Catalytic Performance Synthesized from Cu Nanocube Templates
journal, June 2017


Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes
journal, February 2010

  • Ji, Xiulei; Lee, Kyu Tae; Holden, Reanne
  • Nature Chemistry, Vol. 2, Issue 4, p. 286-293
  • DOI: 10.1038/nchem.553

Shape-Controlled Synthesis of Pd Nanocrystals and Their Catalytic Applications
journal, November 2012

  • Zhang, Hui; Jin, Mingshang; Xiong, Yujie
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar300209w

Bimetallic Palladium−Gold Dendrimer-Encapsulated Catalysts
journal, December 2004

  • Scott, Robert W. J.; Wilson, Orla M.; Oh, Sang-Keun
  • Journal of the American Chemical Society, Vol. 126, Issue 47
  • DOI: 10.1021/ja0475860

The facile synthesis of single crystalline palladium arrow-headed tripods and their application in formic acid electro-oxidation
journal, January 2015

  • Su, Na; Chen, Xueying; Ren, Yuanhang
  • Chemical Communications, Vol. 51, Issue 33
  • DOI: 10.1039/C5CC00353A

Optimierte Nanopartikel-Katalyse für die Sauerstoffreduktionsreaktion
journal, June 2013


Oxygen Reduction on Well-Defined Core−Shell Nanocatalysts: Particle Size, Facet, and Pt Shell Thickness Effects
journal, December 2009

  • Wang, Jia X.; Inada, Hiromi; Wu, Lijun
  • Journal of the American Chemical Society, Vol. 131, Issue 47
  • DOI: 10.1021/ja9067645

Formic acid oxidation on single crystal platinum electrodes. Comparison with polycrystalline platinum
journal, July 1981

  • Clavilier, J.; Parsons, R.; Durand, R.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 124, Issue 1-2
  • DOI: 10.1016/S0022-0728(81)80311-7

Potential, core-level, and d band shifts at transition-metal surfaces
journal, September 1996

  • Ganduglia-Pirovano, M. V.; Natoli, V.; Cohen, M. H.
  • Physical Review B, Vol. 54, Issue 12
  • DOI: 10.1103/PhysRevB.54.8892

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution
journal, May 2017

  • Lu, Fang; Zhang, Yu; Liu, Shizhong
  • Journal of the American Chemical Society, Vol. 139, Issue 21
  • DOI: 10.1021/jacs.7b01735

One-Step Seeding Growth of Magnetically Recyclable Au@Co Core−Shell Nanoparticles: Highly Efficient Catalyst for Hydrolytic Dehydrogenation of Ammonia Borane
journal, April 2010

  • Yan, Jun-Min; Zhang, Xin-Bo; Akita, Tomoki
  • Journal of the American Chemical Society, Vol. 132, Issue 15
  • DOI: 10.1021/ja910513h

Role of Strain and Ligand Effects in the Modification of the Electronic and Chemical Properties of Bimetallic Surfaces
journal, October 2004


Pt-Based Core–Shell Catalyst Architectures for Oxygen Fuel Cell Electrodes
journal, September 2013

  • Oezaslan, Mehtap; Hasché, Frédéric; Strasser, Peter
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 19
  • DOI: 10.1021/jz4014135

Cluster Core-Level Binding-Energy Shifts: The Role of Lattice Strain
journal, July 2004


Shaped Pd–Ni–Pt Core-Sandwich-Shell Nanoparticles: Influence of Ni Sandwich Layers on Catalytic Electrooxidations
journal, June 2014

  • Sneed, Brian T.; Young, Allison P.; Jalalpoor, Daniel
  • ACS Nano, Vol. 8, Issue 7
  • DOI: 10.1021/nn502259g

The Solvent Matters: Kinetic versus Thermodynamic Shape Control in the Polyol Synthesis of Rhodium Nanoparticles
journal, September 2011

  • Biacchi, Adam J.; Schaak, Raymond E.
  • ACS Nano, Vol. 5, Issue 10
  • DOI: 10.1021/nn2026758

Tuning Nanoparticle Catalysis for the Oxygen Reduction Reaction
journal, June 2013

  • Guo, Shaojun; Zhang, Sen; Sun, Shouheng
  • Angewandte Chemie International Edition, Vol. 52, Issue 33
  • DOI: 10.1002/anie.201207186

Towards the computational design of solid catalysts
journal, April 2009

  • Nørskov, J.; Bligaard, T.; Rossmeisl, J.
  • Nature Chemistry, Vol. 1, Issue 1, p. 37-46
  • DOI: 10.1038/nchem.121

New Challenges in Heterogeneous Catalysis for the 21st Century
journal, March 2012


Solvent-Mediated Shape Tuning of Well-Defined Rhodium Nanocrystals for Efficient Electrochemical Water Splitting
journal, May 2017


Decoupling the Geometric Parameters of Shape-Controlled Pd Nanocatalysts
journal, March 2014

  • Laskar, Moitree; Skrabalak, Sara E.
  • ACS Catalysis, Vol. 4, Issue 4
  • DOI: 10.1021/cs401064d

Synthesis and catalytic properties of bimetallic nanomaterials with various architectures
journal, October 2012


Synthesis of Pd−Pt Bimetallic Nanocrystals with a Concave Structure through a Bromide-Induced Galvanic Replacement Reaction
journal, April 2011

  • Zhang, Hui; Jin, Mingshang; Wang, Jinguo
  • Journal of the American Chemical Society, Vol. 133, Issue 15
  • DOI: 10.1021/ja201156s

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.