DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Pt alloy nanoparticles decorated on large-size nitrogen-doped graphene tubes for highly stable oxygen-reduction catalysts

Abstract

Pt alloy nanoparticles supported on Vulcan XC-72 (Pt/C) are the most effective catalysts for kinetically sluggish oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. However, significant performance degradation has been observed with the Pt/C catalysts due to agglomeration and Ostwald ripening of Pt nanoparticles largely resulting from the corrosion of carbon supports. In this paper, we developed a Pt alloy catalyst through annealing Pt nanoparticles deposited on nitrogen/metal co-doped large-size graphene tubes (NGTs). The in-situ formation of PtM (M: Co and Ni) alloy during the annealing process contributes to the improvement of the catalytic activity and stability. During the accelerated stress tests (AST), after 20 000 potential cycles (0.6–1.0 V vs. RHE), the retained electrochemical surface area (ECSA) of the PtM/NGT catalyst is more than 2 times larger than that of the Pt/C catalyst. As for the AST tests of carbon corrosion, after 30 000 potential cycles (1.0–1.5 V vs. RHE) at room temperature, the NGT morphologies are well maintained and no ECSA loss of this PtM catalyst is observed, indicating excellent corrosion-resistance. Even at harsher 60 °C, the PtM/NGT catalyst exhibits only insignificant loss (6 mV) of E1/2 while the Pt/C catalyst shows significant degradation (47 mVmore » loss in E1/2). Finally, the improved stability of PtM/NGT catalyst is attributed to the highly graphitized NGTs and possible synergistic effects between the NGT carbon support and the PtM alloy nanoparticles.« less

Authors:
 [1];  [2];  [1]; ORCiD logo [3];  [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. at Buffalo, NY (United States). Dept. of Chemical and Biological Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  3. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. at Buffalo, NY (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office; USDOE Office of Science (SC)
OSTI Identifier:
1476277
Alternate Identifier(s):
OSTI ID: 1469234
Report Number(s):
BNL-209135-2018-JAAM
Journal ID: ISSN 2040-3364
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 10; Journal Issue: 36; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Chen, Mengjie, Hwang, Sooyeon, Li, Jiazhan, Karakalos, Stavros, Chen, Kate, He, Yanghua, Mukherjee, Shreya, Su, Dong, and Wu, Gang. Pt alloy nanoparticles decorated on large-size nitrogen-doped graphene tubes for highly stable oxygen-reduction catalysts. United States: N. p., 2018. Web. doi:10.1039/C8NR05888A.
Chen, Mengjie, Hwang, Sooyeon, Li, Jiazhan, Karakalos, Stavros, Chen, Kate, He, Yanghua, Mukherjee, Shreya, Su, Dong, & Wu, Gang. Pt alloy nanoparticles decorated on large-size nitrogen-doped graphene tubes for highly stable oxygen-reduction catalysts. United States. https://doi.org/10.1039/C8NR05888A
Chen, Mengjie, Hwang, Sooyeon, Li, Jiazhan, Karakalos, Stavros, Chen, Kate, He, Yanghua, Mukherjee, Shreya, Su, Dong, and Wu, Gang. Mon . "Pt alloy nanoparticles decorated on large-size nitrogen-doped graphene tubes for highly stable oxygen-reduction catalysts". United States. https://doi.org/10.1039/C8NR05888A. https://www.osti.gov/servlets/purl/1476277.
@article{osti_1476277,
title = {Pt alloy nanoparticles decorated on large-size nitrogen-doped graphene tubes for highly stable oxygen-reduction catalysts},
author = {Chen, Mengjie and Hwang, Sooyeon and Li, Jiazhan and Karakalos, Stavros and Chen, Kate and He, Yanghua and Mukherjee, Shreya and Su, Dong and Wu, Gang},
abstractNote = {Pt alloy nanoparticles supported on Vulcan XC-72 (Pt/C) are the most effective catalysts for kinetically sluggish oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. However, significant performance degradation has been observed with the Pt/C catalysts due to agglomeration and Ostwald ripening of Pt nanoparticles largely resulting from the corrosion of carbon supports. In this paper, we developed a Pt alloy catalyst through annealing Pt nanoparticles deposited on nitrogen/metal co-doped large-size graphene tubes (NGTs). The in-situ formation of PtM (M: Co and Ni) alloy during the annealing process contributes to the improvement of the catalytic activity and stability. During the accelerated stress tests (AST), after 20 000 potential cycles (0.6–1.0 V vs. RHE), the retained electrochemical surface area (ECSA) of the PtM/NGT catalyst is more than 2 times larger than that of the Pt/C catalyst. As for the AST tests of carbon corrosion, after 30 000 potential cycles (1.0–1.5 V vs. RHE) at room temperature, the NGT morphologies are well maintained and no ECSA loss of this PtM catalyst is observed, indicating excellent corrosion-resistance. Even at harsher 60 °C, the PtM/NGT catalyst exhibits only insignificant loss (6 mV) of E1/2 while the Pt/C catalyst shows significant degradation (47 mV loss in E1/2). Finally, the improved stability of PtM/NGT catalyst is attributed to the highly graphitized NGTs and possible synergistic effects between the NGT carbon support and the PtM alloy nanoparticles.},
doi = {10.1039/C8NR05888A},
journal = {Nanoscale},
number = 36,
volume = 10,
place = {United States},
year = {Mon Sep 03 00:00:00 EDT 2018},
month = {Mon Sep 03 00:00:00 EDT 2018}
}

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

Citation Metrics:
Cited by: 37 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects
journal, July 2007


The influence of nickel and cobalt on putative members of the oxygen-sensing pathway of erythropoietin-producing HepG2 cells
journal, August 1998


Toxicity of iron and hydrogen peroxide: the Fenton reaction
journal, December 1995


Size-controlled large-diameter and few-walled carbon nanotube catalysts for oxygen reduction
journal, January 2015

  • Wang, Xianliang; Li, Qing; Pan, Hengyu
  • Nanoscale, Vol. 7, Issue 47
  • DOI: 10.1039/C5NR05864C

Pt nanoparticle stability in PEM fuel cells: influence of particle size distribution and crossover hydrogen
journal, January 2009

  • Holby, Edward F.; Sheng, Wenchao; Shao-Horn, Yang
  • Energy & Environmental Science, Vol. 2, Issue 8
  • DOI: 10.1039/b821622n

Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction
journal, January 2015

  • Nie, Yao; Li, Li; Wei, Zidong
  • Chemical Society Reviews, Vol. 44, Issue 8
  • DOI: 10.1039/C4CS00484A

Highly Active and Durable Co-Doped Pt/CCC Cathode Catalyst for Polymer Electrolyte Membrane Fuel Cells
journal, June 2015


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


Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs
journal, March 2005

  • Gasteiger, Hubert A.; Kocha, Shyam S.; Sompalli, Bhaskar
  • Applied Catalysis B: Environmental, Vol. 56, Issue 1-2, p. 9-35
  • DOI: 10.1016/j.apcatb.2004.06.021

Particle size and alloying effects of Pt-based alloy catalysts for fuel cell applications
journal, August 2000


Understanding and approaches for the durability issues of Pt-based catalysts for PEM fuel cell
journal, September 2007


Scientific Aspects of Polymer Electrolyte Fuel Cell Durability and Degradation
journal, October 2007

  • Borup, Rod; Meyers, Jeremy; Pivovar, Bryan
  • Chemical Reviews, Vol. 107, Issue 10
  • DOI: 10.1021/cr050182l

Development of Method for Synthesis of Pt–Co Cathode Catalysts for PEM Fuel Cells
journal, January 2007

  • Li, Xuguang; Colón-Mercado, Héctor R.; Wu, Gang
  • Electrochemical and Solid-State Letters, Vol. 10, Issue 11
  • DOI: 10.1149/1.2777009

High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt
journal, April 2011


Electrocatalyst approaches and challenges for automotive fuel cells
journal, June 2012


Electrochemical Stability of Nanometer-Scale Pt Particles in Acidic Environments
journal, January 2010

  • Tang, Lei; Han, Byungchan; Persson, Kristin
  • Journal of the American Chemical Society, Vol. 132, Issue 2
  • DOI: 10.1021/ja9071496

Activity, stability and degradation of multi walled carbon nanotube (MWCNT) supported Pt fuel cell electrocatalysts
journal, January 2010

  • Hasché, Frédéric; Oezaslan, Mehtap; Strasser, Peter
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 46
  • DOI: 10.1039/c0cp00609b

Raman Spectroelectrochemistry of a Carbon Supercapacitor
journal, January 2001

  • Bonhomme, F.; Lassègues, J. C.; Servant, L.
  • Journal of The Electrochemical Society, Vol. 148, Issue 11
  • DOI: 10.1149/1.1409546

Ordered Pt 3 Co Intermetallic Nanoparticles Derived from Metal–Organic Frameworks for Oxygen Reduction
journal, June 2018


Enhancement of the Electroreduction of Oxygen on Pt Alloys with Fe, Ni, and Co
journal, January 1999

  • Toda, Takako; Igarashi, Hiroshi; Uchida, Hiroyuki
  • Journal of The Electrochemical Society, Vol. 146, Issue 10, p. 3750-3756
  • DOI: 10.1149/1.1392544

Raman spectroscopy in graphene
journal, April 2009


Large Area, Few-Layer Graphene Films on Arbitrary Substrates by Chemical Vapor Deposition
journal, January 2009

  • Reina, Alfonso; Jia, Xiaoting; Ho, John
  • Nano Letters, Vol. 9, Issue 1
  • DOI: 10.1021/nl801827v

Oxygen Reduction on Carbon-Supported Pt−Ni and Pt−Co Alloy Catalysts
journal, April 2002

  • Paulus, U. A.; Wokaun, A.; Scherer, G. G.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 16
  • DOI: 10.1021/jp013442l

Supportless Pt and PtPd Nanotubes as Electrocatalysts for Oxygen-Reduction Reactions
journal, May 2007

  • Chen, Zhongwei; Waje, Mahesh; Li, Wenzhen
  • Angewandte Chemie International Edition, Vol. 46, Issue 22
  • DOI: 10.1002/anie.200700894

Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability
journal, January 2007

  • Stamenkovic, V. R.; Fowler, B.; Mun, B. S.
  • Science, Vol. 315, Issue 5811, p. 493-497
  • DOI: 10.1126/science.1135941

3-D composite electrodes for high performance PEM fuel cells composed of Pt supported on nitrogen-doped carbon nanotubes grown on carbon paper
journal, February 2009


Consumption Rate of Pt under Potential Cycling
journal, January 2007

  • Mitsushima, Shigenori; Kawahara, Shuya; Ota, Ken-ichiro
  • Journal of The Electrochemical Society, Vol. 154, Issue 2
  • DOI: 10.1149/1.2400596

Development of a Titanium Dioxide-Supported Platinum Catalyst with Ultrahigh Stability for Polymer Electrolyte Membrane Fuel Cell Applications
journal, October 2009

  • Huang, Sheng-Yang; Ganesan, Prabhu; Park, Sehkyu
  • Journal of the American Chemical Society, Vol. 131, Issue 39
  • DOI: 10.1021/ja904810h

Nanostructured Pt-alloy electrocatalysts for PEM fuel cell oxygen reduction reaction
journal, January 2010

  • Bing, Yonghong; Liu, Hansan; Zhang, Lei
  • Chemical Society Reviews, Vol. 39, Issue 6
  • DOI: 10.1039/b912552c

A carbon-nanotube-supported graphene-rich non-precious metal oxygen reduction catalyst with enhanced performance durability
journal, January 2013

  • Wu, Gang; More, Karren L.; Xu, Ping
  • Chemical Communications, Vol. 49, Issue 32
  • DOI: 10.1039/c3cc39121c

Effect of nitrogen doping on Raman spectra of multi-walled carbon nanotubes
journal, September 2008

  • Bulusheva, L. G.; Okotrub, A. V.; Kinloch, I. A.
  • physica status solidi (b), Vol. 245, Issue 10
  • DOI: 10.1002/pssb.200879592

Chemisorption of Transition-Metal Atoms on Boron- and Nitrogen-Doped Carbon Nanotubes: Energetics and Geometric and Electronic Structures
journal, April 2009

  • An, Wei; Turner, C. Heath
  • The Journal of Physical Chemistry C, Vol. 113, Issue 17
  • DOI: 10.1021/jp9000913

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation
journal, September 2017

  • Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu
  • Journal of the American Chemical Society, Vol. 139, Issue 40
  • DOI: 10.1021/jacs.7b06514

Raman microprobe studies on carbon materials
journal, January 1994


Influence of Nitrogen Doping on Oxygen Reduction Electrocatalysis at Carbon Nanofiber Electrodes
journal, March 2005

  • Maldonado, Stephen; Stevenson, Keith J.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 10, p. 4707-4716
  • DOI: 10.1021/jp044442z

Development of Highly Active and Durable Hybrid Cathode Catalysts for Polymer Electrolyte Membrane Fuel Cells
journal, January 2014

  • Xie, Tianyuan; Jung, Wonsuk; Kim, Taekeun
  • Journal of The Electrochemical Society, Vol. 161, Issue 14
  • DOI: 10.1149/2.0961414jes

Octahedral PtNi Nanoparticle Catalysts Exceptional Oxygen Reduction Activity by Tuning the Alloy Particle Surface Composition
journal, October 2012

  • Cui, Chunhua; Gan, Lin; Li, Hui-Hui
  • Nano Letters, Vol. 12, Issue 11, p. 5885-5889
  • DOI: 10.1021/nl3032795

Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis
journal, June 2013

  • Cui, Chunhua; Gan, Lin; Heggen, Marc
  • Nature Materials, Vol. 12, Issue 8
  • DOI: 10.1038/nmat3668

Controllable Pt Nanoparticle Deposition on Carbon Nanotubes as an Anode Catalyst for Direct Methanol Fuel Cells
journal, December 2005

  • Mu, Yongyan; Liang, Hanpu; Hu, Jinsong
  • The Journal of Physical Chemistry B, Vol. 109, Issue 47
  • DOI: 10.1021/jp0555448

Recent progress in graphene-based nanomaterials as advanced electrocatalysts towards oxygen reduction reaction
journal, January 2013


Nitrogen doped graphene nanoplatelets as catalyst support for oxygen reduction reaction in proton exchange membrane fuel cell
journal, January 2010

  • Imran Jafri, R.; Rajalakshmi, N.; Ramaprabhu, S.
  • Journal of Materials Chemistry, Vol. 20, Issue 34
  • DOI: 10.1039/c0jm00467g

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells
journal, January 2018

  • Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin
  • Advanced Materials, Vol. 30, Issue 11
  • DOI: 10.1002/adma.201706758

Synthesis of an improved hierarchical carbon-fiber composite as a catalyst support for platinum and its application in electrocatalysis
journal, October 2012


Porous Pt-Ni-P Composite Nanotube Arrays: Highly Electroactive and Durable Catalysts for Methanol Electrooxidation
journal, March 2012

  • Ding, Liang-Xin; Wang, An-Liang; Li, Gao-Ren
  • Journal of the American Chemical Society, Vol. 134, Issue 13
  • DOI: 10.1021/ja212206m

Remarkable support effect of SWNTs in Pt catalyst for methanol electrooxidation
journal, December 2005


Carbon-supported Pt nanoparticles as catalysts for proton exchange membrane fuel cells
journal, January 2005


Enhanced stability of Pt electrocatalysts by nitrogen doping in CNTs for PEM fuel cells
journal, October 2009


The role of nanostructure in nitrogen-containing carbon catalysts for the oxygen reduction reaction
journal, April 2006


An XPS study on oxidation states of Pt and its alloys with Co and Cr and its relevance to electroreduction of oxygen
journal, March 2001


Enhancement of Pt and Pt-alloy fuel cell catalyst activity and durability via nitrogen-modified carbon supports
journal, January 2010

  • Zhou, Yingke; Neyerlin, Kenneth; Olson, Tim S.
  • Energy & Environmental Science, Vol. 3, Issue 10
  • DOI: 10.1039/c003710a

Supportless Pt and PtPd Nanotubes as Electrocatalysts for Oxygen-Reduction Reactions
journal, May 2007


Works referencing / citing this record:

Engineering Local Coordination Environments of Atomically Dispersed and Heteroatom‐Coordinated Single Metal Site Electrocatalysts for Clean Energy‐Conversion
journal, November 2019

  • Zhu, Yuanzhi; Sokolowski, Joshua; Song, Xiancheng
  • Advanced Energy Materials, Vol. 10, Issue 11
  • DOI: 10.1002/aenm.201902844

A Composite Bifunctional Oxygen Electrocatalyst for High‐Performance Rechargeable Zinc–Air Batteries
journal, March 2020


Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation
journal, July 2019


Comparison of the structure and methanol electrooxidation ability from irregular PtNi nanocrystals to PtNiRu nanodendrites
journal, January 2020

  • Li, Zirong; Guan, Zhongyue; Chang, Yuting
  • CrystEngComm, Vol. 22, Issue 8
  • DOI: 10.1039/c9ce01840a

3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: a balance between graphitization and hierarchical porosity
journal, January 2019

  • Qiao, Zhi; Hwang, Sooyeon; Li, Xing
  • Energy & Environmental Science, Vol. 12, Issue 9
  • DOI: 10.1039/c9ee01899a

IrO 2 -incorporated La 0.8 Sr 0.2 MnO 3 as a bifunctional oxygen electrocatalyst with enhanced activities
journal, January 2019

  • Wang, Haizhen; Yan, Litao; Nakotte, Tom
  • Inorganic Chemistry Frontiers, Vol. 6, Issue 4
  • DOI: 10.1039/c9qi00033j

Analytical modeling framework for performance degradation of PEM fuel cells during startup–shutdown cycles
journal, January 2020

  • Li, Yunqi; Chen, Xiran; Liu, Yuwei
  • RSC Advances, Vol. 10, Issue 4
  • DOI: 10.1039/c9ra09572a

Large-diameter and heteroatom-doped graphene nanotubes decorated with transition metals as carbon hosts for lithium–sulfur batteries
journal, January 2019

  • Ogoke, Ogechi; Hwang, Sooyeon; Hultman, Benjamin
  • Journal of Materials Chemistry A, Vol. 7, Issue 21
  • DOI: 10.1039/c9ta02889g

Thermally driven interfacial diffusion synthesis of nitrogen-doped carbon confined trimetallic Pt 3 CoRu composites for the methanol oxidation reaction
journal, January 2019

  • Wang, Qingmei; Chen, Siguo; Lan, Huiying
  • Journal of Materials Chemistry A, Vol. 7, Issue 30
  • DOI: 10.1039/c9ta04412d