Catalytic activity and stability of heat-treated iron phthalocyanines for the electroreduction of oxygen in polymer electrolyte fuel cells

Lalande, G.; Faubert, G; Côté, R.; Guay, Daniel; Dodelet, J. P.; Weng, Lt.; Bertrand, Patrick

doi:10.1016/s0378-7753(96)02356-7

Cited by 153 publications

(126 citation statements)

References 36 publications

Supporting

Mentioning

116

Contrasting

Unclassified

Order By: Relevance

“…The nature of the active site (obtained after heat treatment) in terms of its location on the carbon support (edge versus basal plane) [22], coordination number (Fe-N 4 versus non-Fe-N 4 environment) [23], and chemical identity of the nitrogen functional groups (pyridinic, pyrrolic, and quaternary) [24] have remained a key aspect of intense discussion. Several theories exist to explain the nature of the active site such as those proposed by van Veen et al [25][26][27], McBreen et al [28], Schulenburg et al [29], Yeager et al [2,30], Scherson et al [31][32][33], and Dodelet et al [22,[34][35][36][37][38][39][40][41][42][43][44][45]. Although some authors observed that ORR is conducted by sites comprised of surface nitrogen groups devoid of any metal ion centers [46,47], it is now widely accepted that the transition-metal ion centers coordinated to four nitrogen groups (Me-N 4 ) on graphitic surfaces constitute the active site [22,23,30,48], whereas chelation primarily serves to prevent the metal center from passivation/corrosion under electrochemical conditions [49].…”

Section: Introductionmentioning

confidence: 99%

Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media

Ramaswamy

Mukerjee

2012

Advances in Physical Chemistry

339

255

View full text Add to dashboard Cite

Complex electrochemical reactions such as Oxygen Reduction Reaction (ORR) involving multi-electron transfer is an electrocatalytic inner-sphere electron transfer process that exhibit strong dependence on the nature of the electrode surface. This criterion (along with required stability in acidic electrolytes) has largely limited ORR catalysts to the platinum-based surfaces. New evidence in alkaline media, discussed here, throws light on the involvement of surface-independent outer-sphere electron transfer component in the overall electrocatalytic process. This surface non-specificity gives rise to the possibility of using a wide-range of non-noble metal surfaces as electrode materials for ORR in alkaline media. However, this outer-sphere process predominantly leads only to peroxide intermediate as the final product. The importance of promoting the electrocatalytic inner-sphere electron transfer by facilitation of direct adsorption of molecular oxygen on the active site is emphasized by using pyrolyzed metal porphyrins as electrocatalysts. A comparison of ORR reaction mechanisms between acidic and alkaline conditions is elucidated here. The primary advantage of performing ORR in alkaline media is found to be the enhanced activation of the peroxide intermediate on the active site that enables the complete four-electron transfer. ORR reaction schemes involving both outer-and inner-sphere electron transfer mechanisms are proposed.

show abstract

Section: Introductionmentioning

confidence: 99%

Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media

Ramaswamy

Mukerjee

2012

Advances in Physical Chemistry

339

255

View full text Add to dashboard Cite

show abstract

“…During the last several decades of research into non-noble metal catalysts, heat-treated Fe-and Co-based nitrogen complexes, including porphyrins, phthalocyanines, dibenzotetraazaanulenes, phenanthrolines, polypyrrole, tripyridyl triazine, and so on have been recognized as the most promising candidates for catalyzing the ORR in an acidic medium [3][4][5][6][7][8][9]. It has been found that iron-based complexes can normally catalyze the ORR through a 4-electron reduction pathway to produce water, while cobalt complexes can catalyze a 2-electron reduction pathway [10].I n addition, iron-based catalysts have higher ORR activity than Cobased catalysts but the latter have higher catalytic stability.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of carbon-supported binary FeCo–N non-noble metal electrocatalysts for the oxygen reduction reaction

Kim

Pan

et al. 2010

Electrochimica Acta

View full text Add to dashboard Cite

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.In most cases authors are permitted to post their version of the article (e.g. in Word or Tex form) to their personal website or institutional repository. Authors requiring further information regarding Elsevier's archiving and manuscript policies are encouraged to visit:

show abstract

“…Oxygen saturated 0.5 M H 2 SO 4 was used as the electrolyte. The working electrode fabricated with Fe-based catalysts was as follows [19,20,29,30]. 16 mg of the catalyst, 0.4 ml of H 2 O and 0.4 ml of 5 wt.% Nafion ® (Aldrich) were ultrasonically blended for 10 min.…”

Section: Electrochemical Measurements Andmentioning

confidence: 99%

“…The results were not satisfactory in terms of both the activity and stability of these Co and Fe chelates. Later several research groups reported that the heat-treatment of iron or cobalt macrocycles adsorbed on carbon support improves their activity and stability [15][16][17][18][19][20][21][22]. Moreover, a variety of methods have been employed to prepare electrocatalysts containing iron or cobalt, nitrogen and carbon and exploited them as ORR electrodes [23][24][25].…”

Section: Introductionmentioning

confidence: 99%

Iron and Nitrogen containing Carbon Catalysts with Enhanced Activity for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

Rao¹,

Kumar²,

Viswanathan³

2011

OJPC

View full text Add to dashboard Cite

Iron and nitrogen containing carbon catalysts were prepared by the pyrolysis of iron(III)tetramethoxyphenylporphyrin complex adsorbed on as-received as well as nitric acid treated carbon black and employed them as oxygen reduction electrodes for hydrogen-oxygen PEM fuel cells. The influence of carbon surface functional groups on the dispersion of active species and electrocatalytic performance is investigated using electron microscopic and electrochemical techniques. The existence of quinone functional groups on the nitric acid treated carbon was evident from X-ray photoelectron spectroscopy and cyclic voltammetry. Rotating disk electrode voltammetry results affirmed the good electrocatalytic activity and stability of pyrolyzed macrocyclic complex adsorbed on nitric acid treated carbon compared to that of as-received carbon. This is ascribed to the greater number of Fe/N active species as well as good dispersion of metal clusters over nitric acid treated carbon support. Fuel cell tests depicted the comparable performance of pyrolyzed complex adsorbed on nitric acid treated carbon with commercial Pt/C at 353 K. Durability measurements performed under fuel cell operating conditions for 120 h indicate the good stability of the catalysts.

show abstract

Catalytic activity and stability of heat-treated iron phthalocyanines for the electroreduction of oxygen in polymer electrolyte fuel cells

Cited by 153 publications

References 36 publications

Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media

Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media

Synthesis of carbon-supported binary FeCo–N non-noble metal electrocatalysts for the oxygen reduction reaction

Iron and Nitrogen containing Carbon Catalysts with Enhanced Activity for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

Contact Info

Product

Resources

About