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Title: Dendritic Core-Frame and Frame Multimetallic Rhombic Dodecahedra: A Comparison Study of Composition and Structure Effects on Electrocatalysis of Methanol Oxidation

Abstract

The composition and structure of multimetallic nanostructures can be tailored to enhance electrocatalytic properties. This work reports a seed-mediated synthesis of novel multimetallic dendritic core-frame and frame nanostructures with a rhombic dodecahedral shape for enhanced methanol oxidation reaction (MOR). The synthesis involves in situ formation of Cu seeds and the subsequent selective deposition of Pt and Ru on the edges and vertices of the Cu seeds to generate CuPt and CuPtRu dendritic core-frame nanostructures. The core-frame nanostructures undergo a post acetic acid etching process to form the frame nanostructures. While transmission electron microscopy reveals the morphology and elemental distribution of the nanostructures, X-ray diffraction patterns confirm the alloy compositions of dendritic frames for both the core-frame and frame nanostructures. Compared to the bimetallic CuPt nanostructures, the trimetallic CuPtRu nanostructures lower the onset potential and completely suppress the peak current in the reverse scan for MOR. The CuPtRu alloyed frame nanostructures are the best to prevent Ru leaching compared to the CuPtRu core-frame nanostructures and PtRu catalysts. X-ray photoelectron spectroscopy reveals that all three elements become more electron rich in the frame nanostructures. Thus, further refining the composition ratio of the CuPtRu alloyed dendritic frame nanostructures can lead to more efficientmore » catalysts at a lower cost for MOR.« less

Authors:
 [1];  [2];  [3];  [2];  [2]; ORCiD logo [1]
  1. Univ. of Arkansas, Fayetteville, AR (United States). Dept. of Chemistry and Biochemistry
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF); Univ. of Arkansas, Fayetteville, AR (United States); Arkansas Biosciences Inst., Little Rock, AR (United States)
OSTI Identifier:
1426447
Report Number(s):
BNL-203327-2018-JAAM
Journal ID: ISSN 2199-692X
Grant/Contract Number:  
SC0012704; 1457888
Resource Type:
Accepted Manuscript
Journal Name:
ChemNanoMat
Additional Journal Information:
Journal Volume: 4; Journal Issue: 1; Journal ID: ISSN 2199-692X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 77 NANOSCIENCE AND NANOTECHNOLOGY; metal nanostructures; copper; platinum; ruthenium; nanocrystals

Citation Formats

Mathurin, Leanne E., Tao, Jing, Xin, Huolin, Li, Jun, Zhu, Yimei, and Chen, Jingyi. Dendritic Core-Frame and Frame Multimetallic Rhombic Dodecahedra: A Comparison Study of Composition and Structure Effects on Electrocatalysis of Methanol Oxidation. United States: N. p., 2017. Web. doi:10.1002/cnma.201700249.
Mathurin, Leanne E., Tao, Jing, Xin, Huolin, Li, Jun, Zhu, Yimei, & Chen, Jingyi. Dendritic Core-Frame and Frame Multimetallic Rhombic Dodecahedra: A Comparison Study of Composition and Structure Effects on Electrocatalysis of Methanol Oxidation. United States. https://doi.org/10.1002/cnma.201700249
Mathurin, Leanne E., Tao, Jing, Xin, Huolin, Li, Jun, Zhu, Yimei, and Chen, Jingyi. Fri . "Dendritic Core-Frame and Frame Multimetallic Rhombic Dodecahedra: A Comparison Study of Composition and Structure Effects on Electrocatalysis of Methanol Oxidation". United States. https://doi.org/10.1002/cnma.201700249. https://www.osti.gov/servlets/purl/1426447.
@article{osti_1426447,
title = {Dendritic Core-Frame and Frame Multimetallic Rhombic Dodecahedra: A Comparison Study of Composition and Structure Effects on Electrocatalysis of Methanol Oxidation},
author = {Mathurin, Leanne E. and Tao, Jing and Xin, Huolin and Li, Jun and Zhu, Yimei and Chen, Jingyi},
abstractNote = {The composition and structure of multimetallic nanostructures can be tailored to enhance electrocatalytic properties. This work reports a seed-mediated synthesis of novel multimetallic dendritic core-frame and frame nanostructures with a rhombic dodecahedral shape for enhanced methanol oxidation reaction (MOR). The synthesis involves in situ formation of Cu seeds and the subsequent selective deposition of Pt and Ru on the edges and vertices of the Cu seeds to generate CuPt and CuPtRu dendritic core-frame nanostructures. The core-frame nanostructures undergo a post acetic acid etching process to form the frame nanostructures. While transmission electron microscopy reveals the morphology and elemental distribution of the nanostructures, X-ray diffraction patterns confirm the alloy compositions of dendritic frames for both the core-frame and frame nanostructures. Compared to the bimetallic CuPt nanostructures, the trimetallic CuPtRu nanostructures lower the onset potential and completely suppress the peak current in the reverse scan for MOR. The CuPtRu alloyed frame nanostructures are the best to prevent Ru leaching compared to the CuPtRu core-frame nanostructures and PtRu catalysts. X-ray photoelectron spectroscopy reveals that all three elements become more electron rich in the frame nanostructures. Thus, further refining the composition ratio of the CuPtRu alloyed dendritic frame nanostructures can lead to more efficient catalysts at a lower cost for MOR.},
doi = {10.1002/cnma.201700249},
journal = {ChemNanoMat},
number = 1,
volume = 4,
place = {United States},
year = {Fri Nov 03 00:00:00 EDT 2017},
month = {Fri Nov 03 00:00:00 EDT 2017}
}

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Works referenced in this record:

Seeding a New Kind of Garden: Synthesis of Architecturally Defined Multimetallic Nanostructures by Seed-Mediated Co-Reduction
journal, September 2015

  • Weiner, Rebecca G.; Kunz, Meredith R.; Skrabalak, Sara E.
  • Accounts of Chemical Research, Vol. 48, Issue 10
  • DOI: 10.1021/acs.accounts.5b00300

One-pot fabrication of single-crystalline octahedral Pt–Cu nanoframes and their enhanced electrocatalytic activity
journal, January 2013

  • Nosheen, Farhat; Zhang, Zhi-cheng; Zhuang, Jing
  • Nanoscale, Vol. 5, Issue 9
  • DOI: 10.1039/c3nr00833a

Direct Synthesis of Spatially-Controlled Pt-on-Pd Bimetallic Nanodendrites with Superior Electrocatalytic Activity
journal, June 2011

  • Wang, Liang; Nemoto, Yoshihiro; Yamauchi, Yusuke
  • Journal of the American Chemical Society, Vol. 133, Issue 25
  • DOI: 10.1021/ja202655j

One-Pot Synthesis of Cubic PtCu 3 Nanocages with Enhanced Electrocatalytic Activity for the Methanol Oxidation Reaction
journal, August 2012

  • Xia, Bao Yu; Wu, Hao Bin; Wang, Xin
  • Journal of the American Chemical Society, Vol. 134, Issue 34
  • DOI: 10.1021/ja3051662

Specific adsorption of perchlorate anions on Pt{hkl} single crystal electrodes
journal, January 2014

  • Attard, Gary A.; Brew, Ashley; Hunter, Katherine
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 27
  • DOI: 10.1039/C4CP00564C

Bimetallic Nanocrystals: Syntheses, Properties, and Applications
journal, July 2016


Towards a comprehensive understanding of platinum dissolution in acidic media
journal, January 2014

  • Topalov, Angel A.; Cherevko, Serhiy; Zeradjanin, Aleksandar R.
  • Chem. Sci., Vol. 5, Issue 2
  • DOI: 10.1039/C3SC52411F

Rational Design of Metal Nanoframes for Catalysis and Plasmonics
journal, February 2015


Materials for fuel-cell technologies
journal, November 2001

  • Steele, Brian C. H.; Heinzel, Angelika
  • Nature, Vol. 414, Issue 6861, p. 345-352
  • DOI: 10.1038/35104620

Methanol electro-oxidation by a ternary Pt–Ru–Cu catalyst identified by a combinatorial approach
journal, December 2008


Improved Performance of Direct Methanol Fuel Cells by Anodic Treatment
journal, January 2007

  • Jeon, Min Ku; Won, Jung Yeon; Woo, Seong Ihl
  • Electrochemical and Solid-State Letters, Vol. 10, Issue 1
  • DOI: 10.1149/1.2382260

Bifunctional anode catalysts for direct methanol fuel cells
journal, January 2012

  • Rossmeisl, Jan; Ferrin, Peter; Tritsaris, Georgios A.
  • Energy & Environmental Science, Vol. 5, Issue 8
  • DOI: 10.1039/c2ee21455e

Shape-controlled synthesis of platinum nanocrystals for catalytic and electrocatalytic applications
journal, February 2009


Ag-Enriched Ag-Pd Bimetallic Nanoframes and Their Catalytic Properties
journal, May 2016


A Comparison Study of the Catalytic Properties of Au-Based Nanocages, Nanoboxes, and Nanoparticles
journal, January 2010

  • Zeng, Jie; Zhang, Qiang; Chen, Jingyi
  • Nano Letters, Vol. 10, Issue 1
  • DOI: 10.1021/nl903062e

Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces
journal, February 2014


Polyol Synthesis of Platinum Nanostructures: Control of Morphology through the Manipulation of Reduction Kinetics
journal, April 2005

  • Chen, Jingyi; Herricks, Thurston; Xia, Younan
  • Angewandte Chemie, Vol. 117, Issue 17
  • DOI: 10.1002/ange.200462668

Methanol oxidation and direct methanol fuel cells: a selective review
journal, January 1999


How To Make Electrocatalysts More Active for Direct Methanol OxidationAvoid PtRu Bimetallic Alloys!
journal, October 2000

  • Long, Jeffrey W.; Stroud, Rhonda M.; Swider-Lyons, Karen E.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 42
  • DOI: 10.1021/jp001954e

A review of anode catalysis in the direct methanol fuel cell
journal, April 2006


Synthesis of Pt-Cu Nanodendrites through Controlled Reduction Kinetics for Enhanced Methanol Electro-Oxidation
journal, September 2013


Facile synthesis of PtCu 3 alloy hexapods and hollow nanoframes as highly active electrocatalysts for methanol oxidation
journal, January 2016

  • Xiong, Yaling; Ma, Yanling; Lin, Zhuoqing
  • CrystEngComm, Vol. 18, Issue 40
  • DOI: 10.1039/C6CE01695B

Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces
journal, May 2012

  • Tritsaris, G. A.; Rossmeisl, J.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 22
  • DOI: 10.1021/jp209506d

Oxide stability and chemisorption properties of supported ruthenium electrocatalysts
journal, May 1977

  • Kinoshita, K.; Ross, P. N.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 78, Issue 2
  • DOI: 10.1016/S0022-0728(77)80125-3

Electrocatalysis for Polymer Electrolyte Fuel Cells: Recent Achievements and Future Challenges
journal, April 2012

  • Rabis, Annett; Rodriguez, Paramaconi; Schmidt, Thomas J.
  • ACS Catalysis, Vol. 2, Issue 5
  • DOI: 10.1021/cs3000864

Real surface area measurements in electrochemistry
journal, January 1991


Electrolytic Dissolution of Binary Alloys Containing a Noble Metal
journal, January 1967

  • Pickering, H. W.; Wagner, C.
  • Journal of The Electrochemical Society, Vol. 114, Issue 7
  • DOI: 10.1149/1.2426709

Solution-Based Evolution and Enhanced Methanol Oxidation Activity of Monodisperse Platinum-Copper Nanocubes
journal, May 2009

  • Xu, Dan; Liu, Zhaoping; Yang, Hongzhou
  • Angewandte Chemie International Edition, Vol. 48, Issue 23
  • DOI: 10.1002/anie.200900293

What Are Batteries, Fuel Cells, and Supercapacitors?
journal, October 2004

  • Winter, Martin; Brodd, Ralph J.
  • Chemical Reviews, Vol. 104, Issue 10, p. 4245-4270
  • DOI: 10.1021/cr020730k

One-Pot and Facile Fabrication of Hierarchical Branched Pt–Cu Nanoparticles as Excellent Electrocatalysts for Direct Methanol Fuel Cells
journal, February 2016

  • Cao, Yanqin; Yang, Yong; Shan, Yufeng
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 9
  • DOI: 10.1021/acsami.5b11364

Platinum-Based Oxygen Reduction Electrocatalysts
journal, April 2013

  • Wu, Jianbo; Yang, Hong
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar300359w

Platinum–Ruthenium Nanotubes and Platinum–Ruthenium Coated Copper Nanowires As Efficient Catalysts for Electro-Oxidation of Methanol
journal, February 2015

  • Zheng, Jie; Cullen, David A.; Forest, Robert V.
  • ACS Catalysis, Vol. 5, Issue 3
  • DOI: 10.1021/cs501449y

A Novel Method of Etching Copper Oxide Using Acetic Acid
journal, January 2001

  • Chavez, K. L.; Hess, D. W.
  • Journal of The Electrochemical Society, Vol. 148, Issue 11
  • DOI: 10.1149/1.1409400

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

Reactivity of RuO2 as a promoter for methanol oxidation
journal, October 1990

  • Kennedy, Brendan J.; Smith, Alison W.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 293, Issue 1-2
  • DOI: 10.1016/0022-0728(90)80055-B

Solution-Based Evolution and Enhanced Methanol Oxidation Activity of Monodisperse Platinum-Copper Nanocubes
journal, May 2009


Pt–Ni nanodendrites with high hydrogenation activity
journal, January 2013

  • Wang, Weiyang; Wang, Dingsheng; Liu, Xiangwen
  • Chemical Communications, Vol. 49, Issue 28
  • DOI: 10.1039/c3cc40503f

Kinetically controlled synthesis of Pt–Cu alloy concave nanocubes with high-index facets for methanol electro-oxidation
journal, January 2014

  • Qi, Yue; Bian, Ting; Choi, Sang-Il
  • Chem. Commun., Vol. 50, Issue 5
  • DOI: 10.1039/C3CC48061E

Polyol Synthesis of Platinum Nanostructures: Control of Morphology through the Manipulation of Reduction Kinetics
journal, April 2005

  • Chen, Jingyi; Herricks, Thurston; Xia, Younan
  • Angewandte Chemie International Edition, Vol. 44, Issue 17
  • DOI: 10.1002/anie.200462668

Bimetallic Nanocrystals: Liquid-Phase Synthesis and Catalytic Applications
journal, January 2011


Synthesis of PtCo3 polyhedral nanoparticles and evolution to Pt3Co nanoframes
journal, June 2016


Determination of the Electrochemically Active Surface Area of Metal-Oxide Supported Platinum Catalyst
journal, December 2013

  • Binninger, T.; Fabbri, E.; Kötz, R.
  • Journal of The Electrochemical Society, Vol. 161, Issue 3
  • DOI: 10.1149/2.055403jes

PtCu and PtPdCu Concave Nanocubes with High-Index Facets and Superior Electrocatalytic Activity
journal, December 2011

  • Yin, An-Xiang; Min, Xiao-Quan; Zhu, Wei
  • Chemistry - A European Journal, Vol. 18, Issue 3
  • DOI: 10.1002/chem.201102632

Works referencing / citing this record:

Vertex-Type Engineering of Pt-Cu-Rh Heterogeneous Nanocages for Highly Efficient Ethanol Electrooxidation
journal, September 2018

  • Wang, Kai; Du, Hongyu; Sriphathoorat, Rinrada
  • Advanced Materials, Vol. 30, Issue 45
  • DOI: 10.1002/adma.201804074

Tailoring the Surface Structures of CuPt and CuPtRu 1D Nanostructures by Coupling Coreduction with Galvanic Replacement
journal, April 2018

  • Mathurin, Leanne E.; Benamara, Mourad; Tao, Jing
  • Particle & Particle Systems Characterization, Vol. 35, Issue 5
  • DOI: 10.1002/ppsc.201800053