Metal Carbonyl Cluster Complexes as Electrocatalysts for PEM Fuel Cells

Chapter

Abstract

New mono- and polymetallic electrocatalysts were synthesized from the carbonyl cluster compounds through thermolysis and pyrolysis methods. The precursor compounds used were triosmium dodecacarbonyl [Os3(CO)12], triruthenium dodecacarbonyl [Ru3(CO)12], tetrairidium dodecacarbonyl [Ir4(CO)12], and hexarhodium hexadecacarbonyl [Rh6(CO)16]. In the syntheses by thermolysis, the reaction time (between 5 and 20 h) and the temperature were modified as a function of the solvent used (dimethyl sulfoxide, o-dichlorobenzene, n-nonane, and o-xylene). The pyrolysis variables, including the temperature (90–500 °C), atmosphere gases (nitrogen and hydrogen), and reaction time (controlled at 5 h), were optimized. The precursor compounds and final products were structurally and morphologically characterized using spectroscopic and microscopic analyses. It was found that some of the products showed a metallic character and others were more nonmetallic due to the incorporation of carbonyl groups in their structures. The oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) were measured to evaluate the electrochemical performance of these synthesized electrocatalysts, in the absence and presence of methanol and carbon monoxide, respectively (both contaminants in different concentrations). The materials were tested by rotating disk electrode (RDE), cyclic voltammetry (CV), and linear sweep voltammetry (LSV).

The electrochemical analyses indicated that majority of the electrocatalysts exhibit a dual electrocatalytic behavior toward ORR and HOR. These catalysts are also tolerant to methanol and carbon monoxide, respectively. The synthesized catalysts have superior performance relative to commercial platinum catalysts, which are easily poisoned by CO (ppm). Some iridium-based materials were found to be able to oxidize methanol and ethanol, although their catalytic activity remains to be improved. The most kinetically active catalysts were incorporated into a proton exchange membrane fuel cells (PEMFCs), as part of a Research and Advanced Studies Center, Campus Querétaro (CINVESTAV-Querétaro) fuel cell test system. Under different cell operating conditions, electrical power was generated sufficiently to drive appliances even when a fuel mixture of H2/0.5% CO was introduced. This design opens a new paradigm to apply reforming hydrogen into PEMFCs, with a reduced manufacturing costs and energy balance. The other advantage of this approach is the tolerance of the electrocatalyst to CO, which can poison traditional platinum-based catalysts.

Notes

Acknowledgments

The author thanks V. García-Montalvo and O. Jiménez-Sandoval for their support in his postgraduate research training at the Institute of Chemistry, National Autonomous University of Mexico (UNAM), and CINVESTAV-Querétaro, respectively. C. I. Zuñiga-Romero, A. Mauricio-Sánchez, J. E. Urbina-Alvárez, M. A. Hernández-Landaverde and F. Rodríguez-Melgarejo are acknowledged for technical support; and E. G. Santillán-Rivero is also duly acknowledged for bibliographical assistance (CINVESTAV-Querétaro). The author is grateful to CONACYT for a graduate scholarship and DGAPA-UNAM for a postgraduate fellowship. Finally, the author would like to thank his parents for their invaluable moral support and Miriam Millán-Rocha, for her valuable patience and for accompanying him in this satisfactory experience.

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Centro Nacional de MetrologíaQuerétaroMexico

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