On the electrocatalytical oxygen reduction reaction activity and stability of quaternary RhMo-doped PtNi/C octahedral nanocrystals

Hornberger, Elisabeth; Klingenhof, Malte; Polani, Shlomi; Paciok, Paul; Kormányos, Attila; Chattot, Raphaël; MacArthur, Katherine E.; Wang, Xingli; Pan, Lujin; Drnec, Jakub; Cherevko, Serhiy; Heggen, Marc; Dunin-Borkowski, Rafal E.; Strasser, Peter

doi:10.1039/d2sc01585d

Cited by 13 publications

(10 citation statements)

References 40 publications

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“…The following particles were produced and analyzed in the present work: binary Pt–Ni nanoparticles with 11.7 wt % Pt and an average edge length of 6.6 nm ± 0.7 (denoted PtNi hereafter), Mo-doped PtNi nanoparticles, denoted PtNi(Mo), with 14.9 wt % Pt and an average edge length of 12.4 nm ± 1 (the synthesis protocol is outlined in ref ), and Mo and Rh doped PtNi nanoparticles, denoted PtNi(MoRh), with 14.7 wt % Pt and an average edge length of 8.9 nm ± 0.6, the synthesis protocol is outlined in ref . The PtNi nanoparticles contain about 87% octahedral-shaped particles; the rest have spherical or irregular shapes; the PtNi(Mo) particles contain 93% octahedral particles; and the PtNi(MoRh) particles contain 96% octahedral particles.…”

Section: Methodsmentioning

confidence: 99%

Post-Synthesis Heat Treatment of Doped PtNi-Alloy Fuel-Cell Catalyst Nanoparticles Studied by In-Situ Electron Microscopy

MacArthur

Polani

Klingenhof

et al. 2023

ACS Appl. Energy Mater.

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Octahedral-shaped PtNi-alloy nanoparticles are highly active oxygen reduction reaction catalysts for the cathode in proton exchange membrane fuel cells. However, one major drawback in their application is their limited long-term morphological and compositional stability. Here, we present a detailed in situ electron microscopy characterization of thermal annealing on octahedral-shaped PtNi catalysts as well as on doped octahedral PtNi(Mo) and PtNi(MoRh) catalysts. The evolution of their morphology and composition was quantified during both ex situ and in situ experiments using energy dispersive X-ray spectroscopy in a scanning transmission electron microscope under a hydrogen atmosphere and in vacuum. Morphological changes upon heating, i.e., a gradual loss of the octahedral shape and a continuous rounding of the particles, were observed, as well as evidence for increased alloying. Furthermore, the evolution of the shape of the PtNi(Mo) nanoparticles was quantified using in situ experiments under hydrogen atmosphere in a transmission electron microscope. The shape change of the particles was quantified using segmentation maps created by a neural network. It has been demonstrated that morphological changes crucially depend on the composition and surface doping: doping with Mo or Mo/Rh significantly stabilizes the structure, allowing for persistence of a truncated octahedral shape during heat treatments.

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Section: Methodsmentioning

confidence: 99%

Post-Synthesis Heat Treatment of Doped PtNi-Alloy Fuel-Cell Catalyst Nanoparticles Studied by In-Situ Electron Microscopy

MacArthur

Polani

Klingenhof

et al. 2023

ACS Appl. Energy Mater.

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“…Asset et al used the Rietveld refinement of operando WAXS patterns to track the progressive losses of both global and local strain in hollow PtNi/C catalysts caused by Ni leaching and restructuring during accelerated stress tests . More recently, Hornberger used the same approach to investigate the stability of quaternary RhMo-doped PtNi/C octahedra nanocrystals . The presence of Rh and Mo was found to enhance structural integrity of the particles by suppressing the migration of Pt surface atoms.…”

Section: Electrocatalysismentioning

confidence: 99%

In Situ and Operando X-ray Scattering Methods in Electrochemistry and Electrocatalysis

Magnussen,

Drnec,

Qiu

et al. 2024

Chem. Rev.

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“…Wang et al (2019a) developed a quaternary structurally ordered Pt(Fe,Co,Ni) alloy electrocatalyst with equal proportion of constituent elements via a facile synthesis method that requires spray dehydration on a solid surface followed by annealing procedure. The electrocatalyst showed improved electrocatalytic performance towards ORR with mass activity 6.6 fold higher than that of commercial Pt/C with only 17% attenuation after 10,000 potential cycles at 0.9 V. Hornberger et al (2022) synthesised an octahedral quaternary PtNi(RhMo) alloy electrocatalyst. The alloy electrocatalyst was prepared to control the shape of PtNi by co-doping it with Rh and Mo using solvothermal process.…”

Section: Quaternary Alloy Electrocatalystsmentioning

confidence: 99%

Materials for electrocatalysts in proton exchange membrane fuel cell: A brief review

Alabi

Popoola

et al. 2023

Front. Energy Res.

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Energy is a requisite factor for technological advancement and the economic development of any society. Currently, global energy demand and supply largely rely on fossil fuels. The use of fossil fuels as a source of energy has caused severe environmental pollution and global warming. To salvage the dire situation, research effort is geared toward the utilization of clean, renewable and sustainable energy sources and the hydrogen energy economy is among the most preferred choices. Hydrogen energy economy, which includes hydrogen production, storage and conversion has gained wide consideration as an ecofriendly future energy solution with a fuel cell as its conversion device. Fuel cells, especially, the proton exchange membrane category, present a promising technology that converts hydrogen directly into electricity with great efficiency and no hazardous emissions. Unfortunately, the current generation of proton exchange membrane fuel cells faces some drawbacks that prevent them from large-scale market adoption. These challenges include the high costs and durability concerns of catalyst materials. The main source of high cost in fuel cells is the platinum catalyst used in the electrodes, particularly at the cathode where the sluggish oxygen reduction reaction kinetics require high loading of precious metals. Many research efforts on proton exchange membrane fuel cells are directed to reduce the device cost by reducing or completely replacing the platinum metal loading using alternative low-cost materials with “platinum-like” catalytic behaviour while maintaining high power performance and durability. Consequently, this review attempts to highlight recent research efforts to replace platinum and carbon support with other cost-effective and durable materials in proton exchange membrane fuel cell electrocatalysts. Overview of promising materials such as alloy-based (binary, ternary, quaternary and high-entropy alloys), single atom and metal-free electrocatalysts were discussed, as the research areas are still in their infancy and have many open questions that need to be answered to gain insight into their intrinsic requirements that will inform the recommendation for outlook in selecting them as electrocatalysts for oxygen reduction reaction in proton exchange membrane fuel cell.

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On the electrocatalytical oxygen reduction reaction activity and stability of quaternary RhMo-doped PtNi/C octahedral nanocrystals

Abstract: PtNi nano-octahedra with Rh and Mo dopants are highly active catalysts for the oxygen reduction reaction with excellent stability and shape integrity. We investigate the morphological, structural, and compositional evolution during stability testing.

Cited by 13 publications

References 40 publications

Post-Synthesis Heat Treatment of Doped PtNi-Alloy Fuel-Cell Catalyst Nanoparticles Studied by In-Situ Electron Microscopy

Post-Synthesis Heat Treatment of Doped PtNi-Alloy Fuel-Cell Catalyst Nanoparticles Studied by In-Situ Electron Microscopy

In Situ and Operando X-ray Scattering Methods in Electrochemistry and Electrocatalysis

Materials for electrocatalysts in proton exchange membrane fuel cell: A brief review

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