Electrochemical and Structural Study of a Chemically Dealloyed PtCu Oxygen Reduction Catalyst
Open accessAbstract
A carbon-supported, dealloyed platinum-copper (Pt-Cu) oxygen reduction catalyst was prepared using a multi-step synthetic procedure. Material produced at each step was characterized using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), electron energy loss spectroscopy (EELS) mapping, x-ray absorption spectroscopy (XAS), x-ray diffraction (XRD), and cyclic voltammetry (CV), and its oxygen reduction reaction (ORR) activity was measured by a thin-film rotating disk electrode (TF-RDE) technique. The initial synthetic step, a co-reduction of metal salts, produced a range of poorly crystalline Pt, Cu, and Pt-Cu alloy nanoparticles that nevertheless exhibited good ORR activity. Annealing this material alloyed the metals and increased particle size and crystallinity. TEM shows the annealed catalyst to include particles of various sizes, large (>25 nm), medium (12-25 nm), and small (<12 nm). Most of the small and medium-sized particles exhibited a partial or complete coreshell (Cu-rich core and Pt shell) structure with the smaller particles typically having more complete shells. The appearance of Pt shells after annealing indicates that they are formed by a thermal diffusion mechanism. Although the specific activity of the catalyst material was more than doubled by annealing, the concomitant decrease in Pt surface area resulted in a drop in its mass activity. Subsequent dealloying of the catalyst by acid treatment to partially remove the copper increased the Pt surface area by changing the morphology of the large and some medium particles to a "Swiss cheese" type structure having many voids. The smaller particles retained their core-shell structure. The specific activity of the catalyst material was little reduced by dealloying, but its mass activity was more than doubled due to the increase in surface area. The possible origins of these results are discussed in this report.
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Dealloying resulted in an increase in mass activity from 0.21 to 0.29 A mg-1 Pt at 0.90 V, and an increase in specific activity from 300 to 580 A cm-2 Pt.
“Dealloying resulted in an increase in mass activity from 0.21 to 0.29 A mg -1 Pt at 0.90 V, and an increase in specific activity from 300 to 580 A cm -2 Pt .”
From Carbon-Supported Pt-Based Alloy Electrocatalysts for the Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells: Particle Size, Shape, and Composition Manipulation and Their Impact to Activity (2015) · cites this paper as [281]
The Results and Discussion (RDE measurements; page unavailable) say that dealloying increased mass activity but that specific activity at 0.90 V slightly trailed the annealed sample—not that it rose from 300 to 580. The catalyst-development discussion (page unavailable) reports a dealloyed mass activity of 0.34 A/mg Pt, rather than the claimed 0.29 A/mg Pt. (LLM, conf=0.90)
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Experimental — accuracy not yet measuredThe composition of Pt increased from 20 to 29 wt % while Cu content decreased from 20 to 5.4 wt %.
“The composition of Pt increased from 20 to 29 wt % while the Cu content decreased from 20 to 5.4 wt %.”
From Carbon-Supported Pt-Based Alloy Electrocatalysts for the Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells: Particle Size, Shape, and Composition Manipulation and Their Impact to Activity (2015) · cites this paper as [281]
In Results and Discussion, under “Synthesis and Chemical Characterization” (page not available), the paper says dealloying removed a significant fraction of Cu and raised the Pt/Cu molar ratio from 0.3 to 1.8. That supports the reported change in composition, but the available passage does not give the claimed weight percentages; it points to Table 1 for metal contents. (LLM, conf=0.82)
Experimental — accuracy not yet measuredAfter dealloying, the Pt:Cu molar ratio changed from 0.3 to 1.8 due to removal of copper.
“They found that after dealloying the Pt:Cu molar ratio had changed from 0.3 to 1.8 due to the removal of copper in the dealloying process.”
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Cites
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
Nørskov, J. K., Rossmeisl, J., Logadottir, A., Lindqvist, L., Kitchin, J. R., Bligaard, T., & Jónsson, H. (2004) · The Journal of Physical Chemistry B · doi:10.1021/jp047349j · Cited by 13,153 · see citing works
Gasteiger, H. A., Kocha, S. S., Sompalli, B., & Wagner, F. T. (2005) · Applied Catalysis B: Environmental · doi:10.1016/j.apcatb.2004.06.021 · Cited by 4,876 · see citing works
Stamenkovic, V. R., Fowler, B., Mun, B. S., Wang, G., Ross, P. N., Lucas, C. A., & Marković, N. M. (2007) · Science · doi:10.1126/science.1135941 · Cited by 4,421 · see citing works
Evolution of nanoporosity in dealloying
Erlebacher, J., Aziz, M. J., Karma, A., Dimitrov, N., & Sieradzki, K. (2001) · Nature · doi:10.1038/35068529 · Cited by 2,758 · see citing works
Surface science studies of model fuel cell electrocatalysts
Markovic, N. (2002) · Surface Science Reports · doi:10.1016/s0167-5729(01)00022-x · Cited by 2,145 · see citing works
Transmission Electron Microscopy
Williams, D. B., & Carter, C. B. (1996) · Springer eBooks · doi:10.1007/978-1-4757-2519-3 · Cited by 1,822 · see citing works
Instability of Pt∕C Electrocatalysts in Proton Exchange Membrane Fuel Cells
Ferreira, P. J., la O’, G. J., Shao‐Horn, Y., Morgan, D. D., Makharia, R. R., Kocha, S. S., & Gasteiger, H. A. (2005) · Journal of The Electrochemical Society · doi:10.1149/1.2050347 · Cited by 1,492 · see citing works
Enhancement of the Electroreduction of Oxygen on Pt Alloys with Fe, Ni, and Co
Toda, T., Igarashi, H., Uchida, H., & Watanabe, M. (1999) · Journal of The Electrochemical Society · doi:10.1149/1.1392544 · Cited by 1,336 · see citing works
Mukerjee, S., Srinivasan, S., Soriaga, M. P., & McBreen, J. (1995) · Journal of The Electrochemical Society · doi:10.1149/1.2048590 · Cited by 1,155 · see citing works
Characterization of High‐Surface‐Area Electrocatalysts Using a Rotating Disk Electrode Configuration
Schmidt, T. J., Gasteiger, H. A., Stäb, G. D., Urban, P. M., Kolb, D. M., & Behm, R. J. (1998) · Journal of The Electrochemical Society · doi:10.1149/1.1838642 · Cited by 1,131 · see citing works
Stamenkovic, V. R., Mun, B. S., Mayrhofer, K. J. J., Ross, P. N., & Markovic, N. M. (2006) · Journal of the American Chemical Society · doi:10.1021/ja0600476 · Cited by 974 · see citing works
Particle Size Effects for Oxygen Reduction on Highly Dispersed Platinum in Acid Electrolytes
Kinoshita, K. (1990) · Journal of The Electrochemical Society · doi:10.1149/1.2086566 · Cited by 854 · see citing works
Platinum Monolayer Fuel Cell Electrocatalysts
Adzic, R. R., Zhang, J., Sasaki, K., Vukmirovic, M. B., Shao, M., Wang, J. X., Nilekar, A. U., Mavrikakis, M., Valerio, J. A., & Uribe, F. (2007) · Topics in Catalysis · doi:10.1007/s11244-007-9003-x · Cited by 850 · see citing works
Stamenković, V. R., Schmidt, T. J., Ross, P. N., & Marković, N. M. (2002) · The Journal of Physical Chemistry B · doi:10.1021/jp021182h · Cited by 828 · see citing works
Koh, S., & Strasser, P. (2007) · Journal of the American Chemical Society · doi:10.1021/ja0742784 · Cited by 783 · see citing works
Leapman, R. D., Grunes, L. A., & Fejes, P. (1982) · Physical review. B, Condensed matter · doi:10.1103/physrevb.26.614 · Cited by 700 · see citing works
Zhang, J., Mo, Y., Vukmirovic, M. B., Klie, R. F., Sasaki, K., & Adžić, R. R. (2004) · The Journal of Physical Chemistry B · doi:10.1021/jp0379953 · Cited by 676 · see citing works
Mukerjee, S., & Srinivasan, S. (1993) · Journal of Electroanalytical Chemistry · doi:10.1016/0022-0728(93)80380-z · Cited by 646 · see citing works
An Atomistic Description of Dealloying
Erlebacher, J. (2004) · Journal of The Electrochemical Society · doi:10.1149/1.1784820 · Cited by 641 · see citing works
XAFS spectroscopy; fundamental principles and data analysis
Koningsberger, D. C., Mojet, B. L., van Dorssen, G. E., et al. (2000) · Topics in Catalysis · doi:10.1023/a:1019105310221 · Cited by 524 · see citing works
Grunes, L. A. (1983) · Physical review. B, Condensed matter · doi:10.1103/physrevb.27.2111 · Cited by 496 · see citing works
The oxygen reduction reaction on a Pt/carbon fuel cell catalyst in the presence of chloride anions
Schmidt, T. J., Paulus, U. A., Gasteiger, H. A., & Behm, R. J. (2001) · Journal of Electroanalytical Chemistry · doi:10.1016/s0022-0728(01)00499-5 · Cited by 480 · see citing works
(1989) · De Gruyter eBooks · doi:10.1515/9781501509018 · Cited by 465 · see citing works
Dealloyed Pt−Cu Core−Shell Nanoparticle Electrocatalysts for Use in PEM Fuel Cell Cathodes
Mani, P., Srivastava, R., & Strasser, P. (2008) · The Journal of Physical Chemistry C · doi:10.1021/jp0776412 · Cited by 458 · see citing works
Mukerjee, S., Srinivasan, S., Soriaga, M. P., & McBreen, J. (1995) · The Journal of Physical Chemistry · doi:10.1021/j100013a032 · Cited by 439 · see citing works
Enhancement of the electrocatalytic O2 reduction on Pt–Fe alloys
Toda, T., Igarashi, H., & Watanabe, M. (1999) · Journal of Electroanalytical Chemistry · doi:10.1016/s0022-0728(98)00361-1 · Cited by 429 · see citing works
Mansour, A. N., Cook, J. W., & Sayers, D. E. (1984) · The Journal of Physical Chemistry · doi:10.1021/j150655a029 · Cited by 394 · see citing works
Chen, S., Gasteiger, H. A., Hayakawa, K., Tada, T., & Shao-Horn, Y. (2010) · Journal of The Electrochemical Society · doi:10.1149/1.3258275 · Cited by 360 · see citing works
Murthi, V. S., Urian, R. C., & Mukerjee, S. (2004) · The Journal of Physical Chemistry B · doi:10.1021/jp048985k · Cited by 318 · see citing works
Chen, S., Ferreira, P. J., Sheng, W., Yabuuchi, N., Allard, L. F., & Shao‐Horn, Y. (2008) · Journal of the American Chemical Society · doi:10.1021/ja802513y · Cited by 277 · see citing works
Chen, S., Sheng, W., Yabuuchi, N., Ferreira, P. J., Allard, L. F., & Shao‐Horn, Y. (2008) · The Journal of Physical Chemistry C · doi:10.1021/jp807143e · Cited by 272 · see citing works
Mukerjee, S., & Urian, R. C. (2002) · Electrochimica Acta · doi:10.1016/s0013-4686(02)00242-6 · Cited by 217 · see citing works
Activation Energies for Oxygen Reduction on Platinum Alloys: Theory and Experiment
Anderson, A. B., Roques, J., Mukerjee, S., Murthi, V. S., Markovic, N. M., & Stamenkovic, V. (2005) · The Journal of Physical Chemistry B · doi:10.1021/jp047468z · Cited by 209 · see citing works
Strasser, P., Koh, S., & Greeley, J. (2008) · Physical Chemistry Chemical Physics · doi:10.1039/b803717e · Cited by 208 · see citing works
Teliska, M., Murthi, V. S., Mukerjee, S., & Ramaker, D. E. (2005) · Journal of The Electrochemical Society · doi:10.1149/1.2040949 · Cited by 150 · see citing works
In Situ Scanning Tunneling Microscopy of Corrosion of Silver-Gold Alloys
Oppenheim, I. C., Trevor, D. J., Chidsey, C. E. D., et al. (1991) · Science · doi:10.1126/science.254.5032.687 · Cited by 146 · see citing works
Arruda, T. M., Shyam, B., Ziegelbauer, J. M., et al. (2008) · The Journal of Physical Chemistry C · doi:10.1021/jp8067359 · Cited by 146 · see citing works
Self-citationGupta, G., Slanac, D. A., Kumar, P. R., Wiggins-Camacho, J. D., Wang, X., Swinnea, S., More, K. L., Dai, S., Stevenson, K. J., & Johnston, K. P. (2009) · Chemistry of Materials · doi:10.1021/cm901203n · Cited by 114 · see citing works
Koh, S., Hahn, N. T., Yu, C., & Strasser, P. (2008) · Journal of The Electrochemical Society · doi:10.1149/1.2988741 · Cited by 101 · see citing works
Lucas, C. A., Markovic-acute, N. M., & Ross, P. N. (1997) · Physical review. B, Condensed matter · doi:10.1103/physrevb.55.7964 · Cited by 94 · see citing works
Ferrer, D. A., Blom, D. A., Allard, L. F., et al. (2008) · Journal of Materials Chemistry · doi:10.1039/b801320a · Cited by 71 · see citing works
X-ray absorption spectroscopy in chemistry
Behrens, P. J. (1992) · TrAC Trends in Analytical Chemistry · doi:10.1016/0165-9936(92)87056-p · Cited by 44 · see citing works
Oxygen Reduction by Sol-Derived Pt∕Co-Based Alloys for PEM Fuel Cells
Soderberg, J. N., Sirk, A. H. C., Campbell, S. A., & Birss, V. I. (2005) · Journal of The Electrochemical Society · doi:10.1149/1.2018207 · Cited by 36 · see citing works
Evaluation of a platinum leasing program for fuel cell vehicles
Kromer, M. A., Joseck, F., Rhodes, T., Guernsey, M., & Marcinkoski, J. (2009) · International Journal of Hydrogen Energy · doi:10.1016/j.ijhydene.2009.06.052 · Cited by 27 · see citing works
Early Results from an Aberration-Corrected JEOL 2200FS STEM/TEM at Oak Ridge National Laboratory
Blom, D. A., Allard, L. F., Mishina, S., et al. (2006) · Microscopy and Microanalysis · doi:10.1017/s1431927606060570 · Cited by 26 · see citing works
John, S. S., Dutta, I., & Angelopoulos, A. P. (2010) · The Journal of Physical Chemistry C · doi:10.1021/jp103848n · Cited by 24 · see citing works
Self-citation
Flagged first, then by citations
Research works printed but not linked: 3
- [5]Ross PN Electrocatalysis 1998 Wiley-VCH New York 43
- [29]Stamenkovic V Schmidt TJ Ross PN Markovic NM Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt3Ni and Pt3Co Alloy Surfaces The Journal of Physical Chemistry B 2002 106 46 11970 11979
- [42]Koninsberger DC Prins R X-Ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES 1998 New York Wiley-Interscience 688
Cited by
Sorted by citations
Wang, Y.-J., Zhao, N., Fang, B., Li, H., Bi, X. T., & Wang, H. (2015) · Chemical Reviews · doi:10.1021/cr500519c · Cited by 1,267 · see citing works
Gan, L., Heggen, M., O’Malley, R., Theobald, B., & Strasser, P. (2013) · Nano Letters · doi:10.1021/nl304488q · Cited by 295 · see citing works
Antolini, E. (2017) · Applied Catalysis B: Environmental · doi:10.1016/j.apcatb.2017.05.081 · Cited by 210 · see citing works
Jayasayee, K., Veen, J. A. R. V., Manivasagam, T. G., Celebi, S., Hensen, E. J. M., & de Bruijn, F. A. (2012) · Applied Catalysis B: Environmental · doi:10.1016/j.apcatb.2011.11.003 · Cited by 204 · see citing works
Lattice Strain Distributions in Individual Dealloyed Pt–Fe Catalyst Nanoparticles
Gan, L., Yu, R., Luo, J., Cheng, Z., & Zhu, J. (2012) · The Journal of Physical Chemistry Letters · doi:10.1021/jz300192b · Cited by 140 · see citing works
Gan, L., Cui, C., Rudi, S., & Strasser, P. (2014) · Topics in Catalysis · doi:10.1007/s11244-013-0178-z · Cited by 119 · see citing works
Luo, M., Wei, L., Wang, F., Han, K., & Zhu, H. (2014) · Journal of Power Sources · doi:10.1016/j.jpowsour.2014.07.102 · Cited by 35 · see citing works
- Authors
- Dutta, I., Carpenter, M. K., Balogh, M. P., Ziegelbauer, J. M., Moylan, T. E., Atwan, M. H., & Irish, N. P.
- Affiliations
- General Motors (United States) (US)
- Corresponding author
- Dutta, Indrajit
- Carpenter, Michael K.
- Venue
- The Journal of Physical Chemistry C
- Publisher
- American Chemical Society (ACS)
- Published
- 2010-09-13
- Volume
- 114
- Issue
- 39
- Pages
- 16309-16320
- ISSN
- 1932-7447 (ISSN-L)
- 1932-7455
- PMC
- PMC3691677
- OpenAlex
- W2055956698
- Cited by
- 121
- References
- 46
- Citations by year
- 2025: 1 · 2024: 4 · 2023: 4 · 2022: 3 · 2021: 8 · 2020: 5 · 2019: 5 · 2018: 8 · 2017: 7 · 2016: 8 · 2015: 15 · 2014: 13 · 2013: 15 · 2012: 17
- FWCI
- 6.00
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Locations
- The Journal of Physical Chemistry C (publishedVersion)
- PubMed (publishedVersion)
- Europe PMC (PubMed Central) (acceptedVersion)
- PubMed Central (acceptedVersion)
- Funders
- National Institute of Biomedical Imaging and Bioengineering (P30EB009998)
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
- Physical Sciences › Materials Science › Materials Chemistry › Catalytic Processes in Materials Science
- Physical Sciences › Materials Science › Materials Chemistry › Nanoporous metals and alloys
- Keywords
- PtCu alloy, oxygen reduction reaction, dealloying, core-shell nanoparticles, annealing, thermal diffusion, acid treatment, mass activity, specific activity, platinum surface area, carbon-supported catalysts, nanoparticle morphology
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