Electrocatalysis of CO tolerance in hydrogen oxidation reaction in PEM fuel cells

Lee, S J; Mukerjee, Sanjeev; Ticianelli, Édson Antônio; McBreen, J.

doi:10.1016/s0013-4686(99)00052-3

Cited by 274 publications

(163 citation statements)

References 24 publications

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“…9. The relative activity of the platinum catalyst for 20 ppm CO at 55 • C is about 24% [245], close to that for 100 ppm CO at 80 • C (23%) [246,247] or that for 1% CO at 125 • C (22%). A relative activity around Fig.…”

Section: Poisoning Effect Of Co and Sulphurmentioning

confidence: 51%

High temperature proton exchange membranes based on polybenzimidazoles for fuel cells

Jensen

Savinell

et al. 2009

Progress in Polymer Science

1,242

852

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This article appeared in a journal published by Elsevier. The attached copy is furnished to the author for internal non-commercial research and education use, including for instruction at the authors institution and sharing with colleagues.Other uses, including reproduction and distribution, or selling or licensing copies, or posting to personal, institutional or third party websites are prohibited. To achieve high temperature operation of proton exchange membrane fuel cells (PEMFC), preferably under ambient pressure, acid-base polymer membranes represent an effective approach. The phosphoric acid-doped polybenzimidazole membrane seems so far the most successful system in the field. It has in recent years motivated extensive research activities with great progress. This treatise is devoted to updating the development, covering polymer synthesis, membrane casting, physicochemical characterizations and fuel cell technologies. To optimize the membrane properties, high molecular weight polymers with synthetically modified or N-substituted structures have been synthesized. Techniques for membrane casting from organic solutions and directly from acid solutions have been developed. Ionic and covalent cross-linking as well as inorganic-organic composites has been explored. Membrane characterizations have been made including spectroscopy, water uptake and acid doping, thermal and oxidative stability, conductivity, electro-osmotic water drag, methanol crossover, solubility and permeability of gases, and oxygen reduction kinetics. Related fuel cell technologies such as electrode and MEA fabrication have been developed and high temperature PEMFC has been successfully demonstrated at temperatures of up to 200• C under ambient pressure. No gas humidification is mandatory, which enables the elimination of the complicated humidification system, compared with Nafion cells. Other operating features of the PBI cell include easy control of air flow rate, cell temperature and cooling. The PBI cell operating at above 150• C can tolerate up to 1% CO and 10 ppm SO 2 in the fuel stream, allowing for simplification of the fuel processing system and possible integration of the fuel cell stack with fuel processing units. Long-term durability with a degradation rate of 5 V h −1 has been achieved under continuous operation with hydrogen and air at 150-160• C. With load or thermal cycling, a performance loss of 300 V per cycle or 40 V h −1 per operating hour was observed. Further improvement should be done by, e.g. optimizing the thermal and chemical stability of the polymer, acid-base interaction and acid management, activity and stability of catalyst and more importantly the catalyst support, as well as the integral interface between electrode and membrane.

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Section: Poisoning Effect Of Co and Sulphurmentioning

confidence: 51%

High temperature proton exchange membranes based on polybenzimidazoles for fuel cells

Jensen

Savinell

et al. 2009

Progress in Polymer Science

1,242

852

View full text Add to dashboard Cite

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“…Indeed, it has been demonstrated that Pt-based HT-PEMFC electrodes at 150 °C can tolerate a CO content of about 5000 ppm without significant reduction of the relative catalyst activity [3]. In LT-PEMFC electrodes operated at 85 °C the relative activity was reduced about 30 % by only 20 ppm CO [4].…”

Section: Introductionmentioning

confidence: 99%

Evaluation of temperature and electrolyte concentration dependent Oxygen solubility and diffusivity in phosphoric acid

Fleige

Holst-Olesen

Wiberg³

et al. 2016

Electrochimica Acta

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Reactant diffusion and solubility is of utmost important for providing sufficient reactant concentrations at a catalytic active surface. In high temperature proton exchange membrane fuel cells (HT-PEMFCs) the electrolyte consists of concentrated phosphoric acid embedded into a polybenzimidazole (PBI) membrane. Despite the elevated operation temperature of 150°C, the observed oxygen reduction reaction (ORR) rates in HT-PEMFCs are significantly lower than in low temperature PEMFCs. Reduced reactant transport in combination with site blocking is often mentioned as possible inhibition factors. As a step towards studying the ORR under realistic conditions in half-cell setups, in the present study we investigate the oxygen solubility and diffusivity in diluted phosphoric acid electrolyte in a temperature range of 5 to 80 °C. The presented 2 work demonstrates and discusses under which conditions reliable data for these constants can be obtained. In particular it is shown that the product of oxygen solubility and diffusivity, which determines the oxygen mass transport, first increases as function of temperature, but then decreases again above 60 °C. It seems that the decrease in oxygen solubility at higher temperatures is correlated to an increase in the apparent ORR activation energy.

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“…However, the challenge remains in employing inexpensive reformate hydrogen, wherein the p.p.m.-level of carbon monoxide (CO) impurities can severely deactivate the Pt catalysts [14][15][16] . In addition, although the anode operates at relatively low potentials, its nanocatalysts must be dissolution resistant because of the high potentials experienced during startups and shutdowns 17,18 .…”

mentioning

confidence: 99%

Ordered bilayer ruthenium–platinum core-shell nanoparticles as carbon monoxide-tolerant fuel cell catalysts

et al. 2013

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Fabricating subnanometre-thick core-shell nanocatalysts is effective for obtaining high surface area of an active metal with tunable properties. The key to fully realize the potential of this approach is a reliable synthesis method to produce atomically ordered core-shell nanoparticles. Here we report new insights on eliminating lattice defects in core-shell syntheses and opportunities opened for achieving superior catalytic performance. Ordered structural transition from ruthenium hcp to platinum fcc stacking sequence at the core-shell interface is achieved via a green synthesis method, and is verified by X-ray diffraction and electron microscopic techniques coupled with density functional theory calculations. The single crystalline Ru cores with well-defined Pt bilayer shells resolve the dilemma in using a dissolution-prone metal, such as ruthenium, for alleviating the deactivating effect of carbon monoxide, opening the door for commercialization of low-temperature fuel cells that can use inexpensive reformates (H 2 with CO impurity) as the fuel. O ne major goal in electrocatalysis studies is to produce highly active, durable catalysts, while minimizing the use of precious noble metals, especially platinum (Pt). This is the key requirement for the large-scale commercialization of proton exchange membrane (PEM) fuel cells 1,2 . An effective approach is to fabricate core-shell nanoparticles (NPs) that have active, corrosion-resistant Pt atoms on the surface, with tunable reactivity through their interactions with other metal cores to assure optimal catalytic performances. At the cathode, Pt monolayer (ML) catalysts with Pd or Pd 9 Au alloy cores exhibited enhanced activity and durability for the oxygen reduction reaction compared with Pt NPs 3 . Furthermore, both experimental and theoretical studies verified that lattice contraction 4-7 , high-coordination (111) facets 8-10 and smooth surface morphology 11 are beneficial structural factors in enhancing oxygen reduction reaction activity and the catalysts' durability.For the hydrogen oxidation reaction (HOR) at the anode, a negligible overpotential loss was achieved with pure hydrogen using 50 mg cm À 2 Pt NPs 12,13 . However, the challenge remains in employing inexpensive reformate hydrogen, wherein the p.p.m.-level of carbon monoxide (CO) impurities can severely deactivate the Pt catalysts [14][15][16] . In addition, although the anode operates at relatively low potentials, its nanocatalysts must be dissolution resistant because of the high potentials experienced during startups and shutdowns 17,18 . For developing CO-tolerant HOR catalysts, ruthenium (Ru) was used to support spontaneously deposited sub-ML Pt 19,20 . With about a one-to two-ML-thick Ru(core)-Pt(shell) (denoted as Ru@Pt) NPs, theoretical calculations and temperatureprogrammed measurements showed preferential CO oxidation in hydrogen feeds on Ru@Pt NPs compared with that of Ru-Pt nano-alloys 21 and of Pt shells with other metal core 22 . Besides being a promoter of CO tolerance of Pt surface, Ru ...

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Electrocatalysis of CO tolerance in hydrogen oxidation reaction in PEM fuel cells

Cited by 274 publications

References 24 publications

High temperature proton exchange membranes based on polybenzimidazoles for fuel cells

High temperature proton exchange membranes based on polybenzimidazoles for fuel cells

Evaluation of temperature and electrolyte concentration dependent Oxygen solubility and diffusivity in phosphoric acid

Ordered bilayer ruthenium–platinum core-shell nanoparticles as carbon monoxide-tolerant fuel cell catalysts

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