In situ STM imaging of surface dissolution and rearrangement of a Pt–Fe alloy electrocatalyst in electrolyte solution

Li, Wan; Moriyama, Takahiko; Ito, Megumi; Uchida, Hiroyuki; Watanabe, Masahiro

doi:10.1039/b107037a

Cited by 102 publications

(106 citation statements)

References 13 publications

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“…27,41,74,[89][90][91] Electrochemical scanning tunnelling microscopy (EC-STM) experiments have shown that on a leached PtFe thin film, ordered (111) facets form on the catalyst surface. 92 The vacuum annealed structure was denoted by Stamenkovic et al as a ''Pt-skin'' surface. 89 The Pt overlayer is typically 1 monolayer thick.…”

Section: How To Reach the Peak Of The Volcano?mentioning

confidence: 99%

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Stephens

Bondarenko

Grønbjerg

et al. 2012

Energy Environ. Sci.

1,073

1,024

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The high cost of low temperature fuel cells is to a large part dictated by the high loading of Pt required to catalyse the oxygen reduction reaction (ORR). Arguably the most viable route to decrease the Pt loading, and to hence commercialise these devices, is to improve the ORR activity of Pt by alloying it with other metals. In this perspective paper we provide an overview of the fundamentals underlying the reduction of oxygen on platinum and its alloys. We also report the ORR activity of Pt 5 La for the first time, which shows a 3.5-to 4.5-fold improvement in activity over Pt in the range 0.9 to 0.87 V, respectively. We employ angle resolved X-ray photoelectron spectroscopy and density functional theory calculations to understand the activity of Pt 5 La.

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Section: How To Reach the Peak Of The Volcano?mentioning

confidence: 99%

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Stephens

Bondarenko

Grønbjerg

et al. 2012

Energy Environ. Sci.

1,073

1,024

View full text Add to dashboard Cite

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“…[22][23][24][25][26][27][28][29] For example, the values of j k for Pt-Co alloys showed a maximum at the atomic ratio of Pt/Co = 3. 4,5,14 It has been reported that the electronic structure of the Pt skin layer formed on Pt-M alloys could change with the composition of the underlying alloy, reaching a maximum at the optimum alloy composition or alloying metal species M. 24,[30][31][32] Because the surface is not perfectly covered with uniform Pt skin layer, j k often decreases appreciably by dealloying of M during the operation of PEFCs or electrochemical measurements in acidic electrolyte solutions, particularly at higher temperatures. 14,33 Here, we focus on the influence of crystal structure (ordered and disordered structures) of Pt 3 Co alloy nanoparticles on the ORR activity and durability.…”

mentioning

confidence: 99%

Oxygen Reduction Activity and Durability of Ordered and Disordered Pt₃Co Alloy Nanoparticle Catalysts at Practical Temperatures of Polymer Electrolyte Fuel Cells

Yano¹,

Arima²,

Watanabe³

et al. 2017

J. Electrochem. Soc.

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We have succeeded in preparing ordered-and disordered-Pt 3 Co nanoparticles supported on carbon black (CB), with the nearly identical particle size distribution, by the nanocapsule method with heat-treatment at high temperatures. The temperature dependences of the oxygen reduction reaction (ORR) activities at two kinds of Pt 3 Co/CB catalysts were examined in O 2 -saturated 0.1 M HClO 4 solution by the multi-channel flow double electrode (M-CFDE) technique. For the ordered-Pt 3 Co/CB, the apparent rate constant k app (per unit active area) for the ORR increased with elevation of the temperature up to 65 • C and stabilized at nearly the same value as that for commercial c-Pt/CB at 80 • C, due to a severe dealloying of the Co component in the hot acid solution. In contrast, the k app values at the disordered-Pt 3 Co/CB were higher than those of the ordered-Pt 3 Co/CB over the whole temperature range from 30 • C to 80 • C. The disordered-Pt 3 Co/CB also exhibited higher stability than the ordered-Pt 3 Co/CB for both an accelerated durability test (ADT, by standard potential step cycles between 0.6 V and 1. The polymer electrolyte fuel cell (PEFC) is anticipated to be one of the most promising, clean, and energy-efficient power sources for fuel cell vehicles (FCVs) and stationary cogeneration systems (FCCGs). In 2014, a strategic roadmap for hydrogen and fuel cells was formulated by the Ministry of Economy, Trade, and Industry (METI) of Japan and was revised in 2016.1 For the large scale commercialization of both FCVs and FC-CGs in its Phase 1, it is necessary to reduce the system cost while maintaining the performance and durability. At the present stage, however, the use of substantial amounts of costly Pt cathode catalysts supported on carbon (Pt/C) is unavoidable to decrease the large overpotential for the oxygen reduction reaction (ORR). Hence, the development of the cathode catalysts having both high activity for the ORR and high durability is quite important. To improve the ORR activity, Pt-based catalysts alloyed with non-precious metal such as Fe, 2-6 Co, 2,4,7-11 and Ni, 2-13 have been investigated intensively. For nano-sized Pt-M alloy catalysts (Pt-M/C), the kinetically-controlled area-specific activity j k for the ORR was enhanced by ca. 2∼7 times compared to that of pure Pt. The enhancement factor has been found to depend on various properties of alloy nanoparticles, e.g., composition, 4,14-16 shape (or size), 17-21 and crystal structure. [22][23][24][25][26][27][28][29] For example, the values of j k for Pt-Co alloys showed a maximum at the atomic ratio of Pt/Co = 3. 4,5,14 It has been reported that the electronic structure of the Pt skin layer formed on Pt-M alloys could change with the composition of the underlying alloy, reaching a maximum at the optimum alloy composition or alloying metal species M. 24,[30][31][32] Because the surface is not perfectly covered with uniform Pt skin layer, j k often decreases appreciably by dealloying of M during the operation of PEFCs or electrochemical measurements...

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“…This will be discussed in more detail in Section 3.1.1. [42][43][44][45][46][47][48][49] ard hydrogen electrode by a H 2 SO 4 as used as shown in Fig. 1.…”

Section: Pemfc Cell Reversal Descriptionmentioning

confidence: 99%

Proton Exchange Membrane Fuel Cell Reversal: A Review

et al. 2016

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Abstract:The H 2 /air-fed proton exchange membrane fuel cell (PEMFC) has two major problems: cost and durability, which obstruct its pathway to commercialization. Cell reversal, which would create irreversible damage to the fuel cell and shorten its lifespan, is caused by reactant starvation, load change, low catalyst performance, and so on. This paper will summarize the causes, consequences, and mitigation strategies of cell reversal of PEMFC in detail. A description of potential change in the anode and cathode and the differences between local starvation and overall starvation are reviewed, which gives a framework for comprehending the origins of cell reversal. According to the root factor of cell starvation, i.e., fuel cells do not satisfy the requirements of electrons and protons of normal anode and cathode chemical reactions, we will introduce specific methods to mitigate or prevent fuel cell damage caused by cell reversal in the view of system management strategies and component material modifications. Based on a comprehensive understanding of cell reversal, it is beneficial to operate a fuel cell stack and extend its lifetime.

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In situ STM imaging of surface dissolution and rearrangement of a Pt–Fe alloy electrocatalyst in electrolyte solution

Abstract: The formation of a Pt skin layer with predominantly (111)-oriented facets induced by dissolution of Fe atoms in a Pt-Fe alloy for fuel cell applications is investigated for the first time by using in situ electrochemical STM in 0.1 M HClO4 solution.

Cited by 102 publications

References 13 publications

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Oxygen Reduction Activity and Durability of Ordered and Disordered Pt₃Co Alloy Nanoparticle Catalysts at Practical Temperatures of Polymer Electrolyte Fuel Cells

Proton Exchange Membrane Fuel Cell Reversal: A Review

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In situ STM imaging of surface dissolution and rearrangement of a Pt–Fe alloy electrocatalyst in electrolyte solution

Abstract: The formation of a Pt skin layer with predominantly (111)-oriented facets induced by dissolution of Fe atoms in a Pt-Fe alloy for fuel cell applications is investigated for the first time by using in situ electrochemical STM in 0.1 M HClO4 solution.

Cited by 102 publications

References 13 publications

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Oxygen Reduction Activity and Durability of Ordered and Disordered Pt3Co Alloy Nanoparticle Catalysts at Practical Temperatures of Polymer Electrolyte Fuel Cells

Proton Exchange Membrane Fuel Cell Reversal: A Review

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Oxygen Reduction Activity and Durability of Ordered and Disordered Pt₃Co Alloy Nanoparticle Catalysts at Practical Temperatures of Polymer Electrolyte Fuel Cells