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Fundamental Studies on the Electrocatalytic Properties of Metal Macrocyclics and Other Complexes for the Electroreduction of O2

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Electrocatalysis in Fuel Cells

Part of the book series: Lecture Notes in Energy ((LNEN,volume 9))

Abstract

The high prospects of exploiting the oxygen reduction reaction (ORR) for lucrative technologies, for example, in the fuel cells industry, chlor-alkali electrolysis, and metal-air batteries, to name but a few, have prompted enormous research interest in the search for cost-effective and abundant catalysts for the electrocatalytic reduction of oxygen. This chapter describes and discusses the electrocatalysis of oxygen reduction by metallomacrocyclic complexes and the prospect of their potential to be used in fuel cells. Since the main interest of most researchers in this field is to design catalysts which can achieve facile reduction of O2 at a high thermodynamic efficiency, this chapter aims to bring to light the research frontiers uncovering important milestones towards the synthesis and design of promising metallomacrocyclic catalysts which can accomplish the four-electron reduction of O2 at low overpotential and to draw attention to the fundamental requirements for synthesis of improved catalysts. Particular attention has been paid to discussion of the common properties which cut across these complexes and how they may be aptly manipulated for tailored catalyst synthesis. Therefore, besides discussion of the progress attained with regard to synthesis and design of catalysts with high selectivity towards the four-electron reduction of O2, a major part of this chapter highlights quantitative structure–activity relationships (QSAR) which govern the activity and stability of these complexes, which when well understood, refined, and carefully implemented should lead to rational design of better catalysts. A brief discussion about nonmacrocyclic copper (I) complexes, particularly Cu(I) phenanthrolines, and those with a laccase-like structure which exhibit promising activity for ORR has been included in a separate section at the end.

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Acknowledgments

J.H. Zagal is grateful to Fondecyt 1100773 and Núcleo Milenio Project P07-006 Iniciativa Científica Milenio del Ministerio de Economía, Fomento y Turismo, for financial support. Justus Masa is grateful to the German Academic Exchange Service (DAAD) for a PhD scholarship.

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  1. Analytische Chemie-Elektroanalytik & Sensorik, and Center for Electrochemical Sciences–CES, Ruhr-Universität Bochum, Universitätsstr 150, D-44780, Bochum, Germany

    Justus Masa & Wolfgang Schuhmann

  2. Energy and Process Unit, Materials Science and Manufacturing, Council for Scientific and Industrial Research (CSIR), Pretoria, 0001, South Africa

    Kenneth I. Ozoemena

  3. Department of Chemistry, University of Pretoria, Pretoria, 0002, South Africa

    Kenneth I. Ozoemena

  4. Departamento de Química de los Materiales, Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40, Correo 33, Santiago, 1100773, Chile

    José H. Zagal

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  1. Justus Masa
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  4. José H. Zagal
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    Minhua Shao

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Masa, J., Ozoemena, K.I., Schuhmann, W., Zagal, J.H. (2013). Fundamental Studies on the Electrocatalytic Properties of Metal Macrocyclics and Other Complexes for the Electroreduction of O2 . In: Shao, M. (eds) Electrocatalysis in Fuel Cells. Lecture Notes in Energy, vol 9. Springer, London. https://doi.org/10.1007/978-1-4471-4911-8_7

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